Tomasz Ruman's research while affiliated with Rzeszów University of Technology and other places
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Publications (96)
Purpose:
Bladder cancer (BC) is the 10th most common form of cancer worldwide and the 2nd most common cancer of the urinary tract after prostate cancer, taking into account both incidence and prevalence.
Materials/methods:
Tissues from patients with BC and also tissue extracts were analyzed by laser desorption/ionization mass spectrometry imagin...
Bladder cancer (BC) is a common urological cancer of high mortality and recurrence rates. Currently, cystoscopy is performed as standard examination for the diagnosis and subsequent monitoring for recurrence of the patients. Frequent expensive and invasive procedures may deterrent patients from regular follow-up screening, therefore it is important...
Bladder cancer (BC) is one of the most frequently diagnosed types of urinary cancer. Despite advances in treatment methods, no specific biomarkers are currently in use. Targeted and untargeted profiling of metabolites and elements of human blood serum from 100 BC patients and the same number of normal controls (NCs), with external validation, was a...
Rationale:
3-Hydroxycarboxylic acids are one of the major components of bacterial lipopolysaccharide (LPS) also known as endotoxin. Endotoxins pose a serious health risk and can seriously damage the internal organs of humans and animals. The presented 3-hydroxycarboxylic acids can be used as environmental markers of endotoxin levels. At the time o...
Bladder cancer (BC) is a common urological cancer of high mortality and recurrence rates. Currently, cystoscopy is performed as standard examination for the diagnosis and subsequent monitoring for recurrence of the patients. Frequent expensive and invasive procedures may deterrent patients from regular follow-up screening, therefore it is important...
This study aimed to assess the physicochemical, microbiological and toxicological hazards at an illegal landfill in central Poland. The research included the analysis of airborne dust (laser photometer), the number of microorganisms in the air, soil and leachate (culture method) and the microbial diversity in the landfill environment (high-throughp...
Application of monoisotopic cationic 109Ag nanoparticles (109AgNPs) obtained by PFL (pulsed fiber laser) 2D GS (galvo‐scanner) LGN (laser generated nanomaterial) for both – high resolution laser desorption/ionization mass spectrometry and mass spectrometry imaging of amino acids is presented. Four amino acids, alanine, isoleucine, lysine and phenyl...
Application of monoisotopic cationic ¹⁰⁹Ag nanoparticles (¹⁰⁹AgNPs) obtained by PFL (pulsed fiber laser) 2D GS (galvo-scanner) LASiS (laser ablation synthesis in solution) for high resolution laser desorption/ionization mass spectrometry and mass spectrometry imaging of carboxylic acids is presented. Six acids, azelaic, 3-methylhippuric, linoleic,...
Preparation of gold nanoparticles (AuNPs) by pulsed fiber laser (PFL) laser generated nanomaterial (LGN) with the use of 2D galvo-scanner (2D GS) is described. The procedure of covering of custom-made stainless steel MALDI targets containing studied objects via nebulization is also presented. Examples of application of new method (PFL-2D GS LGN and...
Despite the awareness that work in the sewage treatment plant is associated with biological hazards, they have not been fully recognised so far. The research aims to comprehensively evaluate microbiological and toxicological hazards in the air and settled dust in workstations in a sewage treatment plant. The number of microorganisms in the air and...
Purpose
Renal cell carcinoma (RCC) is a very aggressive and often fatal heterogeneous disease that is usually asymptomatic until late in the disease. There is an urgent need for RCC specific biomarkers that may be exploited clinically for diagnostic and prognostic purposes.
Materials/methods
Serum and urine samples were collected from patients wit...
Preparation of monoisotopic silver-109 nanoparticles (¹⁰⁹AgNPs) by pulsed fiber laser (PFL) ablation synthesis in solution (LASiS) with the use of a 2D galvoscanner (2D GS) is described. The procedure of covering of custom-made stainless-steel MALDI targets containing studied objects via nebulization is also presented. Examples of application of th...
Introduction
Kidney cancer is one of the most frequently diagnosed and the most lethal urinary cancer. Despite advances in treatment, no specific biomarker is currently in use to guide therapeutic interventions.
Objectives
Major aim of this work was to perform metabolomic and elemental profiling of human kidney cancer and normal tissue and to eval...
Kidney cancer is one of the most frequently diagnosed cancers of the urinary tract in the world. Despite significant advances in kidney cancer treatment, no urine specific biomarker is currently used to guide therapeutic interventions. In an effort to address this knowledge gap, metabolic profiling of urine samples from 50 patients with kidney canc...
This study aimed to detect and quantify mycotoxins on building materials using innovative laser mass spectroscopy methods—silver-109/silver/gold nanoparticle-enhanced target surface-assisted laser desorption/ionisation mass spectrometry (109AgNPs, AgNPs and AuNPs SALDI). Results from SALDI-type methods were also compared with commonly used matrix-a...
The aim of this study was to characterise the microbial and metabolite diversity in samples of biodeteriorated 18th century silk from the burial crypts of the Church of St Francis of Assisi in Kraków (Poland). Highthroughput Illumina sequencing, surface-assisted laser desorption/ionisation mass spectrometry on a silver nanoparticle enhanced target...
To date, no method has been developed to assess the distribution of mycotoxins on the surface of grains, or other plant material, and the depth of their penetration into the interior. The Infrared (IR) Laser Ablation-Remote-Electrospray Ionization (LARESI) platform coupled to a tandem mass spectrometer (MS/MS), measuring in selected reaction monito...
Renal cell carcinoma is a very aggressive and often fatal disease for which there are no specific biomarkers found to date. The purpose of work was to find features that differentiate urine metabolic profiles of healthy people and cancer patients. Laser desorption/ionization mass spectrometry on gold nanostructures based techniques was used for the...
The aim of the study was to determine microbial and metabolites diversity on the samples of damaged mediaeval beeswax seals from the Archdiocese Archive of Gniezno, Poland. We employed high-throughput sequencing on the Illumina platform and ¹⁰⁹Ag SALDI metabolome analysis for the first time to assess biodeterioration of the beeswax seals. Bacteria...
Kidney cancer is a disease diagnosed annually in 400,000 people for which there are no specific biomarkers found to date. It is therefore important to search for new chemical compounds to detect cancer state. Laser desorption/ionization mass spectrometry on gold nanoparticle-enhanced target (AuNPET) method was used in this work for rapid metabolic...
Kidney cancer is one of the most frequently diagnosed and the most lethal urinary cancer. Despite all the efforts made, no serum-specific biomarker is currently used in the clinical management of patients with this tumor. In this study, comprehensive high-resolution proton nuclear magnetic resonance spectroscopy (1H NMR) and silver-109 nanoparticle...
A comparison of ionization efficiency for gold and silver nanoparticles used as an active media of matrix‐less laser desorption/ionization (LDI) mass spectrometry (MS) methods was made for carboxylic acids including fatty acids. The MALDI‐type targets containing monoisotopic cationic ¹⁰⁹Ag nanoparticles (¹⁰⁹AgNPs) and Au nanoparticles (AuNPs) were...
Historic photographs are a precious cultural heritage. Despite this, there is a lack of studies on the microorganisms that are responsible for their biodeterioration and the underlying mechanisms. The aims of this study were twofold: (a) assess microorganism diversity on historic photographs using, for the first time, high-throughput sequencing on...
Infrared (IR) Laser Ablation-remote-Electrospray Ionization (LARESI) platform coupled to a tandem mass spectrometer (MS/MS) operated in selected reaction monitoring (SRM) or multiple reaction monitoring (MRM) modes was developed and employed for targeted imaging of selected metabolites in human kidney cancer tissue. The use of SRM or MRM essentiall...
In this work, beeswax was used for the first time for finishing polyester/Cotton/Viscose blend fabric and polyester fabric. The aims of the study were: (1) to characterize the composition of beeswax (using Gas Chromatography Mass Spectrometry, GC-MS and 109AgNPET laser desorption/ionization mass spectrometry (LDI MS); (2) to develop a laboratory me...
Strawberry (Fragaria x ananassa Duch., Rosaceae) is the subject of many research studies due to its numerous features such as unique taste, aroma and health qualities. The distribution of low molecular weight metabolites belonging to aldehydes, ketones, alcohols, esters, organic acids, phenolics, amino acids and sugars classes within strawberry fru...
Aim: Prostate cancer (PCa) is the most commonly diagnosed non-skin cancer among men. Serum prostate-specific antigen level is used as a standard PCa biomarker for over 20 years. However, it has only 33% specificity and 86% sensitivity (for the cutoff value for prostate biopsy of > 4 ng/mL). This leads to overdiagnosis and overtreatment. In-depth in...
Laser desorption/ionization mass spectrometry method on gold nanoparticle enhanced target (AuNPET) was used for rapid detection and quantification of lysine. The amino acid was tested directly in the concentration range from 100 μg/mL to 1 ng/mL, which corresponds to lysine mass of 50 ng to 500 fg per analyzed spot. Detection limit value of 0.2 ng/...
Renal cell carcinoma (RCC) is the most prevalent and lethal malignancy of the kidney. Despite all the efforts made, no tissue biomarker is currently used in the clinical management of patients with kidney cancer. A search for possible biomarkers in urine for clear cell renal cell carcinoma (ccRCC) has been conducted. Non-targeted metabolomic analys...
Surface-assisted laser desorption/ionization mass spectrometry on gold nanoparticle enhanced target (AuNPET) technique was used for metabolomic analysis and secondary metabolites detection of two mould strains – Aspergillus versicolor and Penicillium chrysogenum in model conditions on microbiological malt extract agar medium. Results obtained with...
The aim of this study was to determine the cause of foxing on 19th century paper using omics methods, including metagenomics via high-throughput sequencing on the Illumina platform and metabolomics via high-resolution surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-ToF-MS) imaging using the gold nanoparticle-enh...
A new methodology applicable for both – high resolution laser desorption/ionization mass spectrometry and mass spectrometry imaging of amino acids is presented. The MALDI-type target containing monoisotopic cationic ¹⁰⁹Ag nanoparticles (¹⁰⁹AgNPs) was used for rapid mass spectrometry measurements of eleven amino acids of different chemical propertie...
Aim:
Renal cell carcinoma is a very aggressive and often fatal disease for which there are no specific biomarkers found to date. The purpose of work was to find substances that differentiate the cancerous and healthy tissue by using laser desorption/ionization MS imaging combined with silver nanoparticle-enhanced target.
Results:
Ion images and...
The aim of this study was to compare the metabolite profile of the moulds Alternaria, Aspergillus, Cladosporium, Penicillium, Stachybotrys, and Trichoderma under model conditions on MEA (malt extract agar) medium and carton-gypsum board (CGB). This was followed by comparison of the metabolite profile of each particular strain and of a mixed culture...
Glioblastoma multiforme (GBM) is a central nervous system tumor of grade IV, according to the WHO classification, extremely resistant to all currently used forms of therapy, including resection, radiotherapy, chemotherapy or combined therapy. Therefore, more effective treatment strategies of this tumor are needed, with boron neutron capture therapy...
Laser desorption/ionization mass spectrometry imaging (LDI-MSI) with gold nanoparticle-enhanced target (AuNPET) was used for visualization of small molecules in the rhubarb stalk (Rheum rhabarbarum L.). Analysis was focused on spatial distribution of biologically active compounds which are found in rhubarb species. Detected compounds belong to a ve...
Introduction:
Garlic (Allium sativum) is the subject of many studies due to its numerous beneficial properties. Although compounds of garlic have been studied by various analytical methods, their tissue distributions are still unclear. Mass spectrometry imaging (MSI) appears to be a very powerful tool for the identification of the localisation of...
Introduction:
European yew (Taxus baccata) is a plant known to man for centuries as it produces many interesting and important metabolites. These chemical compounds were repeatedly analysed by various analytical techniques, but none of the methods used so far allowed the localisation of the chemical compounds within the tissue and also correlation...
Renal cell carcinoma (RCC) is a very aggressive and often fatal disease. As many as 30% of patients have metastases to other organs at the moment of diagnosis, so RCC is still a very serious challenge. This is due to its relatively late detection, a problem in which specific markers for RCC could be of great importance. The term biomarker refers to...
Silver nanoparticles (AgNPs) are widely used in all branches of industry. However, their mechanisms of action to moulds have not been studied yet. Thus we conducted this study in which we have used Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (LDI-ToF-MS) analysis to determine the metabolome changes and microscopic analysis (Transmi...
Renal cell carcinoma (RCC) accounts for several percent of all adult malignant tumor cases and is directly associated with over one hundred thousand death cases worldwide annually. Therefore, there is a need for cancer biomarker tests and methods capable of discriminating between normal and malignant tissue. It is demonstrated that gold nanoparticl...
Endogenous thymidylate synthases, isolated from tissues or cultured cells of the same specific origin, have been reported to show differing slow-binding inhibition patterns. These were reflected by biphasic or linear dependences of the inactivation rate on time and accompanied by differing inhibition parameters. Considering importance for chemother...
Gold nanoparticle-enhanced target (AuNPET) was used for detailed investigation of various materials of biological origin - human fingerprint, onion bulb and chicken liver. Analysis of these objects was focused on toxic and harmful compounds - designer drug containing pentedrone, diphenylamine in onion and potentially cancerogenic metronidazole anti...
Boron-neutron capture therapy (BNCT) is a binary anticancer therapy that requires boron compound for nuclear reaction during which high energy alpha particles and lithium nuclei are formed. Unnatural, boron-containing nucleoside with hydrophobic pinacol moiety was investigated as a potential BNCT boron delivery agent. Biological properties of this...
Silver nanoparticles have been successfully applied as matrix replacement for the laser desorption/ionization time-of-flight mass spectrometry (LDI-ToF-MS). Nanoparticles, producing spectra with highly reduced chemical background in low m/z region, are perfectly suited for low-molecular weight compound analysis and imaging. Silver nanoparticles (Ag...
Spektrometria mas (ang. Mass Spectrometry, MS) jest techniką analityczną polegającą na jonizacji substancji obecnych w próbce, a następnie rozdziale powstałych jonów według stosunku masy do ładunku i ich detekcji.
Jednym z najnowszych zastosowań spektrometrii mas jest obrazowanie (ang. Imaging Mass Spectrometry, IMS), dzięki czemu jesteśmy w stani...
A novel synthetic approach is presented, involving unsaturated nucleoside hydroboration, with protected stavudine catalytically boronated with pinacolborane to several pinacolborane derivatives of stavudine or 2',3'-dideoxythymidine. The products were converted to much more stable trifluoroborate derivatives that may be considered trifluoroboron an...
Preparation is described of a durable surface of cationic gold nanoparticles (AuNPs), covering commercial and custom-made MALDI targets, along with characterization of the nanoparticle surface properties and examples of the use in MS analyses and MS imaging (IMS) of low molecular weight (LMW) organic compounds. Tested compounds include nucleosides,...
By seeking new stable boron-containing nucleoside derivatives, potential BNCT boron delivery agents, a novel synthetic approach was tested, aimed at a boron attachment via a single bond to an aliphatic carbon of sp(3) hybridization. The latter allowed successful modification of deoxycytidine in the reaction with 2-(iodomethyl)-4,4,5,5-tetramethyl-1...
Crystal structure is presented of the binary complex between potassium phosphoramidate-phosphorylated recombinant C. elegans thymidylate synthase and dUMP. On each monomer a single phosphoserine residue (Ser127) was identified, instead of expected phosphohistidine. As 31P NMR studies of both the phosphorylated protein and of potassium phosphoramida...
A new method for both - high resolution laser desorption/ionization mass spectrometry and mass spectrometry imaging is described. The method could be considered as matrix-less as no additional matrix is needed for MS measurements and also as SALDI due to nanoparticle-rich surface. The standard MALDI target containing unique monoisotopic cationic 10...
The routes of synthesis of the new boron nucleosides - 3',5'-cyclic boron esters of 2'-deoxycytidine, 2'- deoxyuridine and thymidine along with 3',5'-bis(pinacolborate) derivatives of 2'-deoxyuridine, 5-fluoro-2'- deoxyuridine and thymidine are presented. The 1H-, 13C- and 11B NMR data of new boron nucleosides are compared with their precursors NMR...
Review: major aspects of synthesis, analysis, activity and application
Preparation is described of durable surface of cationic silver nanoparticles (AgNPs), covering commercial and modified MALDI targets, along with characterization of nanoparticles properties and examples of the use in MS analyses of various low molecular weight (LMW) organic compounds, including saccharides, amino acids, nucleosides, glycosides, sul...
Preparation is described of the surface of the first monoisotopic cationic (109)Ag nanoparticles (AgNPs), covering commercial and modified MALDI targets, along with examples of the use in MS analyses of various low-molecular-weight (LMW) organic compounds, including alkaloids, saccharides, amino acids, nucleosides, nucleic bases, and other organics...
A brief overview is presented of major aspects of synthesis, analysis, activity and application of boron analogues and derivatives of biologically active compounds, structurally based on nucleoside/nucleotide skeleton. Comprehensive information on rare boron analogues of nucleic acid bases is also included.
The catalytic hydrogenation of model alkene - cyclohexene with the use of pinacolborane is reported along with the characterization of various side products. The non-standard hydrogenation product was obtained in high yield and purity under very mild reaction conditions with the use of iridium catalyst. The exceptionally high selectivity of the hyd...
Highly purified preparations of thymidylate synthase, isolated from calf thymus, and L1210 parental and FdUrd-resistant cells, were found to be nitrated, as indicated by a specific reaction with anti-nitro-tyrosine antibodies, suggesting this modification to appear endogenously in normal and tumor tissues. Each human, mouse and Ceanorhabditis elega...
This review presents a recent progress in coordination and organometallic chemistry of metal complexes of chelating ligands with pyridine backbone, particularly bidentate [PN] and tridentate [PNP] aminophosphine ligands. The preparation of the ligands, their metal complexes, and the subsequent reactivity studies along with structural properties are...
The nucleus-independent chemical shift (NICS) indices of aromaticity, calculated for four boron compounds, 4-hydroxy-5,6-dihydroborauracil, 4-hydroxyborauracil, borazine and 4-hydroxybenzoborauracil, and parent uracil, were analyzed in parallel with the NMR properties, in order to learn more about the aromaticity of those heterocyclic systems. The...
Preparation and spectroscopic properties of novel boron-containing derivatives of anti-HIV agent stavudine are presented, The new compounds, (5'-O-(4,4,5,5-tetramethyl-1,3,2-dioxaboronate)-2'-3'-didehydro-2'-3'-dideoxythymidine and 5'-O-(dihydroxyboronate)-2'-3'-didehydro-2'-3'-dideoxythymidine), were prepared by direct reaction between stavudine a...
In this paper, we present the detailed study on the correlation of the nuclear magnetic resonance (NMR) parameters with the
results of density functional theory calculations performed for paramagnetic high-spin cobalt(II) complexes with trispyrazolylborate
ligands. This work focuses on estimation of dipolar and contact shifts in mono-ligand high-sp...
Phosphorylation of proteins is an essential signalling mechanism in eukaryotic and prokaryotic cells. Although N-phosphorylation of basic amino acid is known for its importance in biological systems, it is still poorly explored in terms of products and mechanisms. In the present study, two MS fragmentation methods, ECD (electron-capture dissociatio...
Novel 15N-isotope enriched potassium and diammonium thiophosphoramidates were synthesized and their spectroscopic properties, along with reactivity towards several compounds, including histidine, thymidine, glucose and 2- deoxyribose are presented. The application of quantum mechanical DFT calculations for estimation of 31P NMR chemical shifts for...
Thymidylate synthase (TS) may undergo phosphorylation as endogenous protein present in mammalian cells and as recombinant protein (corresponding to human, rat, mouse or Trichinella spiralis TS) expressed in bacterial cells. The phosphorylated, compared to non-phosphorylated, recombinant enzyme forms show decreased (at least by 3-fold) molecular act...
Novel N-15-isotope enriched potassium and diammonium thiophosphoramidates were synthesized and their spectroscopic properties, along with reactivity towards several compounds, including histidine, thymidine, glucose and 2-deoxyribose are presented. The application of quantum mechanical DFT calculations for estimation of P-31 NMR chemical shifts for...
In search of an activity-preserving protein thiophosphorylation method, with thymidylate synthase recombinant protein used as a substrate, potassium thiophosphoramidate and diammonium thiophosphoramidate salts in Tris- and ammonium carbonate based buffer solutions were employed, proving to serve as a non-destructive environment. Using potassium pho...
Synthesis of 4-hydroxyborauracil and 4-hydroxy-3-methylborauracil, the first boron analogues of uracil, and comparison of their 1H and 13C NMR properties with those of uracil, are presented. The analyses of NMR-monitored boron compound-alcohol and boron compound-amine interactions pointed to the existence of sp3-hybridized, B,B-bis-methoxyborauraci...
Novel boron compounds, a series of 4-hydroxy-5,6-dihydroborauracil and 4-hydroxy-5,6-dihydroborathymine derivatives containing various substituents at 3-, 5- and 6-positions, is presented. The spectroscopic properties, along with analyses of NMR-controlled boron compound-alcohol and boron compound-amine interactions, proves the existence of sp(3)-h...
Novel boron compounds - 5,6-saturated borauracil derivatives (4-bromo-5,6-dihydroborauracil, 4-hydroxy-5,6-dihydroborauracil and 4-methoxy-5,6-dihydroborauracil) are presented along with other boron compounds obtained from N-vinylurea: N-substituted beta-boronic amino acid - 2-{[(dihydroxyborano-amino)(dihydroxyboranooxy)methyl]-amino}ethylboronic...
We present a detailed study on the correlation of the nuclear magnetic resonance (NMR) parameters with the results of density
functional theory (DFT) calculations performed for paramagnetic high-spin cobalt(II) complexes with trispyrazolylborate ligands.
This work is a first attempt to calculate dipolar and contact shifts in high-spin cobalt(II) py...
During the last few decades microporous and mesoporous materials have been considered for medical use due to biological properties and stability in biological environment. Zeolites have been investigated as drug carriers, and as adjuvants in anticancer therapy, dietetic supplements or antimicrobial agents. This review gives a brief overview of the...
Hydroxyborohydride (sodium and potassium salts) were prepared by a one-pot method and the H-1 NMR spectrum of sodium hydroxyborohydride was recorded for the first time. Based on an NMR experiment, hydroxyborohydride was found to be more reactive toward acetone carbonyl than borohydride. The calculated B-11- and B-10-H coupling constants are in very...
This review gives a brief overview over the major aspects of application of the nicotine alkaloid and its close derivatives in the therapy of some neurodegenerative disorders and diseases (e.g. Alzheimer's disease, Parkinson's disease, Tourette's syndrome, schizophrenia etc.). The issues concerning methods of nicotine analysis and isolation, and so...
Thallium(I) complexes of heteroscorpionate hydrobis(3-phenyl-5-methylpyrazolyl)(3,5-dimethylpyrazol-yl)borate and hydrotris(3-phenylpyrazol-1-yl)borate were studied crystallographically. Both ligands were coordinated in κ3 fashion via N2 atoms of pyrazol-1-yl moieties. Both compounds crystallize as centrosymmetric dimers in which weak CH/π intra- a...
The structure of Tp″Rh(NBD) complex was determined by X-ray crystallography (Tp″=hydrobis(3-phenyl-5-isopropylpyrazolyl)(3,5-dimethylpyrazolyl)borate, NBD=2,5-norbornadiene). The Tp″ was found to be κ3 coordinated to rhodium(I). Two independent molecules of Tp″Rh(NBD) were found in triclinic crystals with Rh–N(pz) distances in the region of 2.113(3...
Condensation of 5(3)-isopropyl-3(5)-phenylpyrazole with sodium borohydride led to a mixture of tris(pyrazolyl)borate ligands (Tpx) − the homoscorpionate hydrotris(5-isopropyl-3-phenylpyrazolyl)borate and the heteroscorpionates hydro(3-isopropyl-5-phenylpyrazolyl)bis(5-isopropyl-3-phenylpyrazolyl)borate and hydrobis(3-isopropyl-5-phenylpyrazolyl)(5-...
Tetra(3-iso-propylpyrazol-1-yl)borate ligand (L) forms mono-ligand LMX and bis-ligand L2M complexes (where M=Ni(II), and Cu(II), and X=Cl- or NO3-) depending on the stoichiometry of the synthesis, while a polynuclear (NCS)2Co(L)Co(L)Co(NCS)2 complex is obtained when excess of cobalt(II) thiocyanate is used. The L coordinates to metal ions in a 3 fa...
The synthesis of the sodium salt of a new anionic heteroscorpionate trispyrazolylborate ligand as of sodium hydrobis(3-phenyl,5-methylpyrazolyl)(3,5-diethylpyrazolyl)borate (NaTp″) was described. Two cobalt(II) complexes: Tp″Co(NCS)(THF) and Tp″CoTp were synthesized and characterized crystallographically. Trispyrazolylborate ligands (Tp″ and Tp) ar...
Heteroscorpionate Tp‘ ‘ ligands constructed of two 3-phenyl-5-methylpyrazolyl and a variable third pyrazolyl residue (3-methyl-5-phenyl-, 3,5-dimethyl-, and 3,5-diethylpyrazolyl) coordinate to rhodium(I) in a κ2 fashion to form Tp‘ ‘Rh(LL) complexes (where LL = COD or (CO)2). One of the two 3-phenyl-5-methylpyrazolyl and the less sterically hindere...
The synthesis of hydrotris(pyrazol-1-yl)borate ligands (Tpx) by condensation of sodium borohydride with 3(5)-isopropylpyrazole and either 5(3)-methyl-3(5)-phenylpyrazole or 3,5-diphenylpyrazole gave the novel heteroscorpionate ligands hydrobis(5-methyl-3-phenylpyrazolyl)(5-isopropylpyrazolyl)borate and hydrobis(3,5-diphenylpyrazolyl)(5-isopropylpyr...
The synthesis of hydrotris(pyrazol-1-yl)borate ligands (Tp(x)) by condensation of sodium borohydride with 3(5)-isopropylpyrazole and either 5(3)-methyl-3(5)-phenylpyrazole or 3,5-diphenylpyrazole gave the novel heteroscorpionate ligands hydrobis(5-methyl-3-phenylpyrazolyl)(5-isopropylpyrazolyl)- borate and hydrobis(3,5-diphenylpyrazolyl)(5-isopropy...