Dominique Agustin

Publications

• 4.66

  Impact points

  Rational Synthesis and Characterization of the Mixed-Metal Organometallic Polyoxometalates [Cp*Mo(x)W(6-x)O(18)](-) (x = 0, 1, 5, 6).

  Gülnur Taban-Çalışkan, Daniel Mesquita Fernandes, Jean-Claude Daran, Dominique Agustin, Funda Demirhan, Rinaldo Poli

  Inorganic chemistry. 04/2012;

  The reaction between the oxometallic complexes Cp*(2)M(2)O(5) and Na(2)M'O(4) (M, M' = Mo, W) in a 1:10 molar ratio in an acidic aqueous medium constitutes a mild and selective entry into the anionic Lindqvist-type hexametallic organometallic mixed oxides [Cp*Mo(x)W(6-x)O(18)](-) [x = 6 (1),... [more] The reaction between the oxometallic complexes Cp*(2)M(2)O(5) and Na(2)M'O(4) (M, M' = Mo, W) in a 1:10 molar ratio in an acidic aqueous medium constitutes a mild and selective entry into the anionic Lindqvist-type hexametallic organometallic mixed oxides [Cp*Mo(x)W(6-x)O(18)](-) [x = 6 (1), 5 (2), 1 (3), 0 (4)]. All of these compounds have been isolated as salts of nBu(4)N(+) (a), nBu(4)P(+) (b), and Ph(4)P(+) (c) cations and two of them (1 and 3) also with the n-butylpyridinium (nBuPyr(+), d) cation. The compounds have been characterized by elemental analyses, thermogravimetric analyses, electrospray mass spectrometry, and IR spectroscopy. The molecular identity and geometry of compounds 1c, 2a, and 2c have been confirmed by single-crystal X-ray diffraction. Density functional theory calculations on models obtained by replacing Cp* with Cp (I-IV) have provided information on the assignment of the terminal M═O and bridging M-O-M vibrations.
• 2.21

  Impact points

  Charged dioxomolybdenum(VI) complexes with pyridoxal thiosemicarbazone ligands as molybdenum(V) precursors in oxygen atom transfer process and epoxidation (pre)catalysts

  Jana Pisk, Biserka Prugovecki, Dubravka Matkovic-Calogovic, Rinaldo Poli, Dominique Agustin, Višnja Vrdoljak

  Polyhedron. 01/2012; 33:441-449.

  The reaction of [MoO2(acac)2] with hydrochloric salts of pyridoxal thiosemicarbazone ligands, H2L1–3.HCl, in dry methanol or acetonitrile resulted in the formation of the mononuclear complex [MoO2(HL1)(CH3OH)]Cl.1.5CH3OH (1a) or polynuclear complexes [{MoO2(HL1–3)}Cl]n (1–3) containing a different s... [more] The reaction of [MoO2(acac)2] with hydrochloric salts of pyridoxal thiosemicarbazone ligands, H2L1–3.HCl, in dry methanol or acetonitrile resulted in the formation of the mononuclear complex [MoO2(HL1)(CH3OH)]Cl.1.5CH3OH (1a) or polynuclear complexes [{MoO2(HL1–3)}Cl]n (1–3) containing a different substituent on the nitrogen atom of the N-thioureide fragment: Ph (1 and 1a), Me (2) or H (3). New dinuclear molybdenum(V) complexes [Mo2O3(HL1–3)2]Cl2 (4–6) were obtained by oxygen atom abstraction from 1–3 with triphenylphosphine. All compounds were characterized by chemical analysis, IR spectroscopy, one- and two-dimensional NMR methods, TGA and in selected cases by DSC measurements. In addition, the crystal and molecular structure of 1a was determined by single crystal X-ray diffraction. All molybdenum(VI) species were used as (pre)catalysts for olefin epoxidation under solvent-free conditions with a 0.05% Mo loading versus olefin.
• 5.19

  Impact points

  Epoxidation Processes by Pyridoxal Dioxomolybdenum(VI) (Pre)Catalysts Without Organic Solvent

  Jana Pisk, Dominique Agustin, Višnja Vrdoljak, Rinaldo Poli

  Advanced Synthesis & Catalysis. 01/2011; 353:2910-2914.

  Molybdenum(VI) pyridoxal thiosemicarbazonato complexes have proved to be efficient catalysts in the olefinic epoxidation of cyclooctene by aqueous TBHP in the absence of an organic solvent. High activity and selectivity have been obtained with a catalyst loading of just 0.05% molybdenum in the case ... [more] Molybdenum(VI) pyridoxal thiosemicarbazonato complexes have proved to be efficient catalysts in the olefinic epoxidation of cyclooctene by aqueous TBHP in the absence of an organic solvent. High activity and selectivity have been obtained with a catalyst loading of just 0.05% molybdenum in the case of one mononuclear (pre)catalyst (TOF 3360 h−1) under solvent-free conditions. The influence of methanol on the activity and selectivity has been studied.
• 2.32

  Impact points

  Oxo-bridged bis oxo-vanadium(V) complexes with tridentate Schiff base ligands (VOL)2O (L = SAE, SAMP, SAP): Synthesis, structure and epoxidation catalysis under solvent-free conditions

  Cindy Cordelle, Dominique Agustin, Jean-Claude Daran, Rinaldo Poli

  Inorganica Chimica Acta. 01/2010; 364:144-149.

  The dinuclear V(V) complexes (VOL)2O (L = SAE (1), SAMP (2), SAP (3)) have been synthesized from VO(acac)2 and the corresponding tridentate ligands LH2 in methanol under reflux conditions and subsequent air oxidation in organic solvent. They have been characterized by IR and NMR spectroscopy, by the... [more] The dinuclear V(V) complexes (VOL)2O (L = SAE (1), SAMP (2), SAP (3)) have been synthesized from VO(acac)2 and the corresponding tridentate ligands LH2 in methanol under reflux conditions and subsequent air oxidation in organic solvent. They have been characterized by IR and NMR spectroscopy, by thermogravimetric analysis, and by single crystal X-ray diffraction for 1 and 2. DFT calculations were carried out for a better understanding of the vibrational pattern, principally the V–O related vibrations. Complex [VO(SAP)]2O (3) catalyzes the epoxidation of cyclooctene by TBHP in water in the absence of any added solvent with good selectivity.
• 1.23

  Impact points

  Structural Characterization and Theoretical Calculations of cis-Dioxo(N-salicylidene-2-aminophenolato)(ethanol)molybdenum(VI) Complexes MoO2(SAP)(EtOH) (SAP = N-salicylidene-2 aminophenolato)

  Dominique Agustin, Christine Bibal, Benjamin Neveux, Jean-Claude Daran, Rinaldo Poli

  Zeitschrift für anorganische und allgemeine Chemie. 01/2009; 635:2120-2125.

  The crystal structure of MoO2(SAP)(EtOH) is reported for the first time. The compound crystallizes in the monoclinic crystallographic system (P21/n, a = 11.0923(3) Å, b = 6.9590(2) Å, c = 19.4499(5) Å, β = 94.458(1)°, V = 1496.82(7) Å3, Z = 4). The molybdenum atom adopts a distorted octahedral arran... [more] The crystal structure of MoO2(SAP)(EtOH) is reported for the first time. The compound crystallizes in the monoclinic crystallographic system (P21/n, a = 11.0923(3) Å, b = 6.9590(2) Å, c = 19.4499(5) Å, β = 94.458(1)°, V = 1496.82(7) Å3, Z = 4). The molybdenum atom adopts a distorted octahedral arrangement with cis Mo=O bonds, typical for cis-dioxomolybdenum(VI) complexes. The ethanol ligand is situated trans to one oxido ligand. Theoretical calculations in the gas phase were performed to examine the relative stability of MoO2(L)(EtOH) and the [MoO2(L)]2 dimeric form (L = SAP, SAE).
• 2.94

  Impact points

  Rational, Facile Synthesis and Characterization of the Neutral Mixed-Metal Organometallic Oxides Cp*2MoxW6-xO17 (Cp* = C5Me5, x = 0, 2, 4, 6)

  Gülnur Taban-Çaliskan, Dominique Agustin, Funda Demirhan, Laure Vendier, Rinaldo Poli

  European Journal of Inorganic Chemistry. 01/2009; 2009:5219 - 5226.

  The reaction of the bis(pentamethylcyclopentadienyl)pentaoxidodimetal complexes Cp*2M2O5 with four equivalents of Na2M'O4 (M, M' = Mo, W) in acidic aqueous medium constitutes a soft and selective entry into neutral Lindqvist-type organometallic mixed-metal oxides Cp*2MoxW6-xO17 [x = 6 (1), 4... [more] The reaction of the bis(pentamethylcyclopentadienyl)pentaoxidodimetal complexes Cp*2M2O5 with four equivalents of Na2M'O4 (M, M' = Mo, W) in acidic aqueous medium constitutes a soft and selective entry into neutral Lindqvist-type organometallic mixed-metal oxides Cp*2MoxW6-xO17 [x = 6 (1), 4 (2), 2 (3), 0 (4)]. The identity of the complexes is demonstrated by elemental analyses, thermogravimetric analyses and infrared spectroscopy. Thermal degradation of 1-4 up to above 500 °C leads to Mox/6W1-/6O3. The molecular identity and geometry of compound 2 is further confirmed by a fit of the powder X-ray diffraction pattern with a model obtained from previously reported single-crystal X-ray structures of 1 and 4, with which 2 is isomorphous. DFT calculations on models obtained by replacing Cp* with Cp (I-IV) validate the structural assignments and assist in the assignment of the M,M'-O vibrations.
• 1.58

  Impact points

  119Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands

  Dominique Agustin, Markus Ehses

  Comptes Rendus Chimie. 01/2009; 10:1189 - 1227.

  The coordination effect of transition metal TML n (L = co-ligand) on stannylenes R 2 SnB n (B = base, n = 0–2) has been examined analysing 119 Sn NMR data and X-ray molecular structures from the literature up to 2008. Coordination deshielding Δ δ ( 119 Sn) and chemical shift δ ( 119 Sn) of B n R 2 S... [more] The coordination effect of transition metal TML n (L = co-ligand) on stannylenes R 2 SnB n (B = base, n = 0–2) has been examined analysing 119 Sn NMR data and X-ray molecular structures from the literature up to 2008. Coordination deshielding Δ δ ( 119 Sn) and chemical shift δ ( 119 Sn) of B n R 2 Sn–TM(CO) n complexes, linearly correlate with δ ( 119 Sn) of R 2 Sn. Slope, intercept and typical regions are interpreted through different ratios of σ/π-back bonding and impact of TM, R and B n . Hybridisation changes explain dependencies of 1 J Sn–TM coupling constants on L, R, B n and TM gyromagnetic ratios γ TM . The Sn–TM bond lengths follow a parabolic profile along the TM period, fine-tuned by R, B and L n . Electronic modifications on carbonyl complexes classify R 2 Sn as poor π-acceptors, while shortening of Sn–R and widening of angles R–Sn–R correspond to increased s-character of the Sn–TM bond. A “coordinative Lewis base radius” r coord (SnR 2 ) of 1.18 Å is proposed.
• 0.78

  Impact points

  Polymorph of {2-[(2-hydroxyethyl)iminiomethyl]phenolato-kappaO}dioxido{2-[(2-oxidoethyl)iminomethyl]phenolato-kappa3O,N,O'}molybdenum(VI).

  Dominique Agustin, Jean-Claude Daran, Rinaldo Poli

  Acta crystallographica. Section C, Crystal structure communications. 02/2008; 64(Pt 2):m101-4.

  A second polymorphic form (form I) of the previously reported compound {2-[(2-hydroxyethyl)iminiomethyl]phenolato-kappaO}dioxido{2-[(2-oxidoethyl)iminomethyl]phenolato-kappa(3)O,N,O'}molybdenum(VI) (form II), [Mo(C(9)H(9)NO(2))O(2)(C(9)H(11)NO(2))], is presented. The title structure differs from... [more] A second polymorphic form (form I) of the previously reported compound {2-[(2-hydroxyethyl)iminiomethyl]phenolato-kappaO}dioxido{2-[(2-oxidoethyl)iminomethyl]phenolato-kappa(3)O,N,O'}molybdenum(VI) (form II), [Mo(C(9)H(9)NO(2))O(2)(C(9)H(11)NO(2))], is presented. The title structure differs from the previously reported polymorph [Głowiak, Jerzykiewicz, Sobczak & Ziółkowski (2003). Inorg. Chim. Acta, 356, 387-392] by the fact that the asymmetric unit contains three molecules linked by O-H...O hydrogen bonds. These trimeric units are further linked through O-H...O hydrogen bonds to form a chain parallel to the [111] direction. As in the previous polymorph, each molecule is built up from an MoO(2)(2+) cation surrounded by an O,N,O'-tridentate ligand (O(-)C(6)H(4)CH=NCH(2)CH(2)O(-)) and weakly coordinated by a second zwitterionic ligand (O(-)C(6)H(4)CH=N(+)HC(2)H(4)OH). All complexes are chiral with the absolute configuration at Mo being C or A. The main difference between the two polymorphs results from the alternation of the chirality at Mo within the chain.
• 2.35

  Impact points

  Synthesis, Characterisation and Study of the Chromogenic Properties of the Hybrid Polyoxometalates [PW11O39(SiR)2O]3- (R = Et,(CH2)nCH=CH2(n=0,1,4), CH2CH2SiEt3,CH2CH2SiMe2Ph)

  Dominique Agustin, Jérôme Dallery, Cristina Coelho, Anna Proust, René Thouvenot

  Journal of Organometallic Chemistry. 01/2007; 692:746-754.

  Reaction of Cl3SiR or (EtO)3SiR with [PW11O39]7− affords the disubstituted hybrid anions [PW11O39(SiR)2O]3−. These species have been characterized by IR spectroscopy in the solid state and by multinuclear NMR (1H, 29Si, 31P and 183W) and cyclic voltammetry in solution. The hydrosilylation of [PW11O3... [more] Reaction of Cl3SiR or (EtO)3SiR with [PW11O39]7− affords the disubstituted hybrid anions [PW11O39(SiR)2O]3−. These species have been characterized by IR spectroscopy in the solid state and by multinuclear NMR (1H, 29Si, 31P and 183W) and cyclic voltammetry in solution. The hydrosilylation of [PW11O39(Si–CHdouble bond; length as m-dashCH2)2O]3− has been achieved with Et3SiH and PhSiMe2H. These are the first examples of hydrosilylation on a hybrid tungstophosphate core. The chromogenic behaviour of hybrid species has been demonstrated in solution.
• 1.23

  Impact points

  Organic-Inorganic Hybrids based on Polyoxometalates. Part 8. Synthesis and Spectroscopic Characterization of the Heterosilylated Anions [PW9O34(tBuSiO)3(SiR)]3- (R = CH3, -CH=CH2, -CH2-CH=CH2, (CH2)4-CH=CH2) - ...

  Dominique Agustin, Cristina Coelho, Agnès Mazeaud, Patrick Herson, Anna Proust, René Thouvenot

  Zeitschrift für anorganische und allgemeine Chemie. 01/2004; 630:2049-2053.

  The reaction of the open-structure anion PW9O34((BuSiOH)-Bu-t)(3)(3-) with RSiCl3 (R = (CH2)(n)CH=CH2 (n = 0, 1, 4)) affords PW9O34((BuSiO)-Bu-t)(3)(SiR)(3-) heterosilylated capped hybrid compounds. These complexes were characterized by infrared spectroscopy and in solution by multinuclear (H-1, Si-... [more] The reaction of the open-structure anion PW9O34((BuSiOH)-Bu-t)(3)(3-) with RSiCl3 (R = (CH2)(n)CH=CH2 (n = 0, 1, 4)) affords PW9O34((BuSiO)-Bu-t)(3)(SiR)(3-) heterosilylated capped hybrid compounds. These complexes were characterized by infrared spectroscopy and in solution by multinuclear (H-1, Si-29, P-31 and W-183) NMR. Crystals of (Bu4N)-Bu-n(3)PW9O34((BuSiO)-Bu-t)(3)Si(CH2-CH=CH2) are orthorhombic, space group P2(1)2(1)2(1) (Ndegrees 19), with lattice constants a = 15.599(2) Angstrom, b = 23.963(5) Angstrom, c = 26.886(1) Angstrom, V = 10.050(3) Angstrom(3), and Z = 4.
• 2.35

  Impact points

  Functional tetraarylstannanes Sn[C6H4-R]4 (R = -CH(CH2O)2, -CH=O, -COOH, -CH=N-NH-C6H4-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3, -CH[N(C2H4)2O]2)

  Michael Veith, Andreas Rammo, Christian Kirsch, Lucie Khemtémourian, Dominique Agustin

  Journal of Organometallic Chemistry. 01/2004; 689:1546-1552.

  Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C6H4-CH(OCH2)2]4 (2), which was transformed to Sn[C6H4-CHO]4 (3) and its hydrazido and amino derivatives Sn[C6H4-CH=N--NH-C6H3-2,4-(NO2)2]4 (5) and Sn{C6H4-CH[N(C2H4)2O]2}4 (8). Oxidation of (3) produced Sn[C6H4-COOH]4 (4) w... [more] Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C6H4-CH(OCH2)2]4 (2), which was transformed to Sn[C6H4-CHO]4 (3) and its hydrazido and amino derivatives Sn[C6H4-CH=N--NH-C6H3-2,4-(NO2)2]4 (5) and Sn{C6H4-CH[N(C2H4)2O]2}4 (8). Oxidation of (3) produced Sn[C6H4-COOH]4 (4) while reduction of (3) gave Sn[C6H4-CH2-OH]4 (6). From the acid 4. an amino acid Sn[C6H4-CO-NH-CH2-CO-OCH3]4 (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).
• 2.35

  Impact points

  New Synthetic Approach and Structural Characterization of the Chloroalkylstannanes (Cl-CH2)nSnCl4-n (n=2,4) and the Hydrolysis Product [(Cl-CH2)2Sn(Cl)-O-Sn(Cl)(CH2Cl)2]2

  Michael Veith, Dominique Agustin, Volker Huch

  Journal of Organometallic Chemistry. 01/2002; 646:138-145.

  The chloroalkylstannanes Cl2Sn(CH2Cl)2 (1) and Sn(CH2Cl)4 (3) have been prepared in high yields by the treatment of tin tetrachloride with diazomethane under the elimination dinitrogen. The established synthetic process was modified in such a way, that the yields were considerably upgraded and the i... [more] The chloroalkylstannanes Cl2Sn(CH2Cl)2 (1) and Sn(CH2Cl)4 (3) have been prepared in high yields by the treatment of tin tetrachloride with diazomethane under the elimination dinitrogen. The established synthetic process was modified in such a way, that the yields were considerably upgraded and the isolation of the products simplified: instead of using CH2N2 in solution, CH2N2 was transported by a nitrogen gas flow in a special apparatus. The compounds 1 and 3 were crystallized and their crystal and molecular structures were obtained (for 1 this was a redetermination) by X-ray diffraction [1: orthorhombic; space group: Pmmn; a = 7.760(2), b = 10.190(2), c = 4.840(1) Å; V = 382.7 Å3; Z=2. 3: monoclinic; space group: C2/c; a = 9.849(2), b = 9.872(2), c = 10.611(2) Å, β = 96.30(3)°; V = 988.3 Å3; Z = 4]. Both molecular compounds are connected in the solid state by either intermolecular Sn...Cl interactions (1) or weak H...Cl bridges (3). In the crystal structure of 1 the molecules adopt almost perfect C2, symmetry (the twofold axis bisecting the Cl-Sn-Cl angle) and stack together in such a way, that all chlorine atoms are oriented in one direction. The two tin bonded chlorine atoms form an SnCl2 scissor which chelates the neighboring molecule via the two Sn...Cl contacts (3.76 A) upgrading the coordination number at tin from 4 to 6. This feature can best be seen from the increase of the C-Sn-C bond angle to 135.4° (instead of tetrahedral) and from the simultaneous decrease of Cl-Sn-Cl to 98.9°. In the crystal of 3 the central tin atom is almost tetrahedrally coordinated by four carbon atoms, but there are still weak intermolecular interactions caused by H...Cl bridges (3.01 Å). Treatment of compound 1 with moisture converts it to the chlorostannoxane (ClCH2)2ClSn-O-SnCl(CH2Cl)2 (2) which turns out to crystallize as a distinct centrosymmetric dimer. Compound 2 crystallizes in the monoclinic space group P21/n (a = 8.842(2), b = 18.704(4), c = 8.693(2) Å, β = 109.48(3)°. V = 1352.3 Å3, Z = 2) and the dimeric molecule deviates from the typical ladder like structure of chlorostannoxanes with the three adjacent four-membered cycles (SnClOSn, Sn2O2, SnClOSn) by further Sn...Cl interaction (3.450 Å). Through this interaction all tin, tin bonded chlorines and oxygen atoms become assembled within a common plane which is wrapped up by eight CH2Cl-groups above and below this plane (overall point symmetry almost C2b). The ten atoms (4Sn, 4Cl. 2O) can also be described as two oxygen centered interpenetrating Cl2Sn3O distorted hexagons. The tin atoms are either in trigonal bipyramidal or octahedral distorted coordination spheres, while the oxygen atoms are trigonal planarly coordinated by three tin atoms.
• 4.20

  Impact points

  Ligand transfer reactions between (Schiff Base) Divalent Group 14 Element species and titanium, nickel, boron and phosphorous halides.

  Dominique Agustin, Ghassoub Rima, Heinz Gornitzka, Jacques Barrau

  Organometallics. 01/2000; 19:4276-4282.

  Reactions of the inorganic complexes TiCl4, NiCl2, BF3, PCl3, and (Y)PCl3 (Y = O, S), Cp2TiCl2, and t-BuPCl2 with the Schiff base divalent group 14 element species (L2)M (1−3: L2 = N,N‘-bis(salicylidene)ethylenediamine (Salen), M = Ge (1), Sn (2); L2 = (R,R)-(−)-N,N‘-bis(3,5-di-tert-butylsalicyliden... [more] Reactions of the inorganic complexes TiCl4, NiCl2, BF3, PCl3, and (Y)PCl3 (Y = O, S), Cp2TiCl2, and t-BuPCl2 with the Schiff base divalent group 14 element species (L2)M (1−3: L2 = N,N‘-bis(salicylidene)ethylenediamine (Salen), M = Ge (1), Sn (2); L2 = (R,R)-(−)-N,N‘-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine, M = Pb (3)) have been investigated. TiCl4 and Cp2TiCl2 afforded the ionic [ClTi(L2)]+[MCl3]- (4) and the neutral Cp(Cl)Ti(L2) (5) complexes, respectively. With NiCl2·DPPE (DPPE = 1,2-bis(diphenylphosphino)ethane) and (Salen)Sn as starting materials, substitution of tin led to the complex (Salen)Ni·SnCl2 (7). The linear diboron compound F2B(Salen)BF2 (9) together with the complex (Salen)Sn·SnF2 (10) were produced on reaction of BF3·Me2O with (Salen)Sn. With t-BuPCl2 and PCl3, the phosphite t-BuP(L2) (11) and the phosphocation [(L2)P]+ (12) together with the anion [MCl3]- (9) were obtained, respectively. The phosphoryl and thiophosphoryl chlorides (Y)PCl3 (Y = O, S) yielded the dinuclear dimeric phosphoranes (Y = O (13), S (14)). The crystal structure of 3 was determined by X-ray structure analysis.
• 4.66

  Impact points

  (Schiff Base) Divalent Group 14 Element Species Manganese and Iron Complexes [(Salen)M]Mn(C5H5)(CO)2 (M = Ge, Sn, Pb) and [(Salen)Sn]Fe(CO)4

  Dominique Agustin, Ghassoub Rima, Heinz Gornitzka, Jacques Barrau

  Inorganic Chemistry. 01/2000; 39:5492-5495.

  Syntheses of the (divalent group 14 species)dicarbonyl(cyclopentadienyl)manganese (Salen)MMn(CO)2(η5-C5H5) [M = Ge (1), Sn (2), Pb (3)] and [(Salen)tin(II)]tetracarbonyliron (Salen)SnFe(CO)4 (4) are reported. The structures of 2 and 4 were determined by X-ray crystallography. The observed Sn−Mn bond... [more] Syntheses of the (divalent group 14 species)dicarbonyl(cyclopentadienyl)manganese (Salen)MMn(CO)2(η5-C5H5) [M = Ge (1), Sn (2), Pb (3)] and [(Salen)tin(II)]tetracarbonyliron (Salen)SnFe(CO)4 (4) are reported. The structures of 2 and 4 were determined by X-ray crystallography. The observed Sn−Mn bond length, 2.4428(7) Å, is the shortest distance observed for this type of bond and corresponds to considerable multiple bonding between these atoms. In complex 4, the iron atom has a slightly distorted trigonal-bipyramidal coordination sphere; the (Salen)tin(II) ligand occupies an axial site, indicating that it functions in this complex as a strong σ-donor and weak π-acceptor ligand. Crystal data for 2: orthorhombic, P212121, a = 6.972(1) Å, b = 15.678(2) Å, c = 19.032(2) Å, α = β = γ = 90°, V = 2080.3(5) Å3, T = 173(2) K, Z = 4. Crystal data for 4: triclinic, P , a = 8.465(2) Å, b = 9.795(3) Å, c = 13.213(4) Å, α = 105.55(3)°, β = 105.15(3)°, γ = 100.84(3)°, V = 978.7(5) Å3, T = 173(2) K, Z = 2.
• 2.94

  Impact points

  Transition Metal Complexes of (Schiff Base)Divalent Group 14 Element Species [(Salen)M]nM’(CO)6-n, (n= 1, 2 ; M= Ge, Sn, Pb; M’ = Cr ,W)

  Dominique Agustin, Ghassoub Rima, Heinz Gornitzka, Jacques Barrau

  European Journal of Inorganic Chemistry. 01/2000; 2:693-702.

  The syntheses, characterization, and reactivities of the new stable mono- and cis-disubstituted Group 14 metal(II) chromium and tungsten carbonyl complexes (salen)M=M′(CO)5 [salen = 2,2′-N,N′-bis(salicylidene)ethylenediamine; M′ = Cr, M = Ge (4), Sn (5), Pb (6); M′ = W, M = Ge (7), Sn (8), Pb (9)] a... [more] The syntheses, characterization, and reactivities of the new stable mono- and cis-disubstituted Group 14 metal(II) chromium and tungsten carbonyl complexes (salen)M=M′(CO)5 [salen = 2,2′-N,N′-bis(salicylidene)ethylenediamine; M′ = Cr, M = Ge (4), Sn (5), Pb (6); M′ = W, M = Ge (7), Sn (8), Pb (9)] and [(salen)M]2=M′(CO)4 [M′ = W, M = Ge (10), Sn (11), Pb (12); M′ = Cr, M = Sn (14), Ge (15)] are described. Complexes 4–9 were obtained in high yields by treatment of the M′(CO)5 · THF intermediates with the stable divalent species (salen)MII [M = Ge (1), Sn (2), Pb (3)]. Direct irradiation of mixtures of (salen)MII and M′(CO)6 resulted in formation of the monosubstituted compounds 4–9 together with the disubstituted species 10–12, 14, and 15 in ratios depending on the nature of both M and M′. Pure complexes 10–12 were obtained by two different synthetic approaches starting from the (salen)MII species or the (salen)M=M′(CO)5 complexes. Each of the new complexes has been characterized by 1H- and 13C-NMR, and by 119Sn-NMR in the case of 5, 8, 11, and 14, as well as by IR spectroscopy in all cases. The molecular structures of 5, 8, 11, and 14, determined by X-ray structure analyses, reveal a pentacoordinated tin atom. The tin–chromium distances are among the shortest (in particular that in 5, 2.557 Å) observed for transition metal divalent tin complexes and the tin lies about 0.99 Å above the plane defined by the O2N2 atoms of the salen ligand. All these complexes have been found to be unreactive towards water and organic acids. Simple phosphane monosubstitution of carbonyl in 8 using Ph3P led to the new complex 13. Reactions with 1,2-bis(diphenylphosphanyl)ethane and 3,5-di-tert-butyl-1,2-benzoquinone resulted in displacement of the divalent species from the carbonyl complexes 5 and 8.
• 0.22

  Impact points

  Espèces du groupe 14 à ligand Base de Schiff de type (Base de Schiff)M=E (M = Ge, Sn ; E = N-SiMe3,S,Se)

  Dominique Agustin, Ghassoub Rima, Heinz Gornitzka, Jacques Barrau

  Main group metal chemistry. 01/1999; 22:703-711.

  The reactions of the divalent species (LM)-M-2 (L-2 = tetradentate Schiff base; M = Ge, Sn) with Me3SiN3, elemental S-8 or Se have resulted in the isolation of the new stable formal metallanimines, metallanethiones and -selones (LM)-M-2=E (E = N-SiMe3, S, Se). All these compounds have been physicoch... [more] The reactions of the divalent species (LM)-M-2 (L-2 = tetradentate Schiff base; M = Ge, Sn) with Me3SiN3, elemental S-8 or Se have resulted in the isolation of the new stable formal metallanimines, metallanethiones and -selones (LM)-M-2=E (E = N-SiMe3, S, Se). All these compounds have been physicochemically and chemically characterized. Their reactions with 3,5-di-tert-butyl-1,2-benzoquinone produced new dioxametalloles, A substitution reaction of chalcogen (S/Se) has been observed indicating that the energies of the M=Se bonds are lower than those of the M=S bonds. The molecular structure of the stannylene (Salen)Sn was determined by X-ray cristallographic analysis; in this compound the tin atom has a distorted square pyramidal geometry with the Salen ligand occupying the base plane.
• 2.35

  Impact points

  Stable Heterocyclic Schiff Base Divalent M14 Species M-O-(Schiff Base)-O (M = Ge, Sn, Pb),

  Dominique Agustin, Ghassoub Rima, Heinz Gornitzka, Jacques Barrau

  Journal of Organometallic Chemistry. 01/1999; 592:1-10.

  The synthesis and characterization of new stable divalent germanium, tin and lead homoleptic species L2M [L2=2,2′-N,N′-bis(salicylidene)ethylenediamine, M=Ge (1), Sn (2), Pb (3); (R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine, M=Ge (4), Sn (5), Pb (6) and N-methyl-2,2′-imin... [more] The synthesis and characterization of new stable divalent germanium, tin and lead homoleptic species L2M [L2=2,2′-N,N′-bis(salicylidene)ethylenediamine, M=Ge (1), Sn (2), Pb (3); (R,R)-(−)-N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine, M=Ge (4), Sn (5), Pb (6) and N-methyl-2,2′-imino-bis(8-hydroxyquinoline), M=Ge (7), Sn (8)] are described. Compounds 1–8 were obtained in good yields by alcoholysis of the M---N bonds of the divalent precursors [(Me3Si)2N]2M by diols with bis(salicylidene)diamine and 2,2′-imino-bis-quinoline structures. They have been isolated as solids at ambient temperature and are monomeric. NMR, IR and UV spectra are suggestive of Ncdots, three dots, centeredM intramolecular coordination. The chemistry of 1–8 is illustrated through their reactions with iodine and 1,2-benzoquinones. The X-ray structure of the L2Sn-quinone adduct reveals a distorted octahedral coordination geometry around tin with remarkably short Sn---N distances. Various R---CH=O insertion reactions into the M---O bonds of 1–8 and M---O cleavage reactions with organic acids and acyl halides are also described; they provide a convenient procedure for the generation of new heteroleptic divalent species.
• 0.22

  Impact points

  New heterocyclic bivalent tin and germanium species (Schiff’s base)M(II) (M = Ge,Sn) and related metallanethiones and -selones.

  Dominique Agustin, Ghassoub Rima, Jacques Barrau

  Main group metal chemistry. 01/1997; 20:791-793.

  The syntheses of new stable bivalent homoleptic germanium and tin species L2M (L-2 = (R,R)-(-)-N,N'-bis(3,5-di-tert-salicylidene)-1,2-cyclohexanediamine, M = Ge (1), M = Sn (2); L-2 = N,N'-bis(salicylidene) ethylenediamine, M = Ge (3), M = Sn (4); L-2 = N-methyl-2,2'-imino-bis(8-hydroxyq... [more] The syntheses of new stable bivalent homoleptic germanium and tin species L2M (L-2 = (R,R)-(-)-N,N'-bis(3,5-di-tert-salicylidene)-1,2-cyclohexanediamine, M = Ge (1), M = Sn (2); L-2 = N,N'-bis(salicylidene) ethylenediamine, M = Ge (3), M = Sn (4); L-2 = N-methyl-2,2'-imino-bis(8-hydroxyquinoline), M = Ge (5), M = Sn (6) are described. New stable linear or cyclic organometallic compounds and metallanethiones and -selones L2M=E (E = S, Se) are obtained starting from 1-4.