Enrique Pérez Carreño

University of Oviedo | UNIOVI · Department of Physical and Analytical Chemistry

E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds = N(SiMe3)2, bqfam = N,N′-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from the formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a and 1b are fluxional in solution at room temperature, as the E atom os...

The bis(amidinato)-heavier tetrylenes E(bzamP)2 (E = Ge (2a) and Sn (2b); bzamP = N-isopropyl-N'-(diphenylphosphanylethyl)benzamidinate), which are equipped with one heavier tetrylene (germylene or stannylene) and two phosphane fragments (one on each amidinate moiety) as coordinable groups, have been synthesized from the benzamidinum salt [H2bzamP]...

The dipyrromethane‐based chloridogermyl complexes [MCl{κ³P,Ge,P‐GeCl(pyrmPⁱPr2)2CMe2}] (1M; M=Ni, Pd; (pyrmPⁱPr2)2CMe2=5,5’‐dimethyl‐2,2’‐bis(di‐isopropylphosphanylmethyl)dipyrromethane‐1,1’‐diyl) reacted with one or more equivalents of LiOMe to give the monosubstituted complexes [MCl{κ³P,Ge,P‐Ge(OMe)(pyrmPⁱPr2)2CMe2}] (2M−OMe; M=Ni, Pd). However,...

An unusual T-shaped palladium(0) complex having a σ-acceptor ( Z -type) germylene scaffold has been prepared from a dipyrromethane-based PGeP germylene.

The stable phosphane-functionalized heavier tetrylenes E(tBu2bzam)pyrmPtBu2 (E = Si (1Si), Ge (1Ge); tBu2bzam = N,N’-ditertbutylbenzamidinate; HpyrmPtBu2 = ditertbutyl(2-pyrrolylmethyl)phosphane) have been prepared by reacting the amidinatotetrylenes E(tBu2bzam)Cl (E = Si, Ge) with LipyrmPtBu2. The reactions of 1Si and 1Ge with selected M⁰ and MII...

Reactions of the mesityl(amidinato)tetrylenes E(tBu2bzam)Mes (tBu2bzam = N,N′-bis(tert-butyl)benzamidinate; Mes = mesityl; E = Ge (1Ge), Si (1Si)) with the iridium precursors [Ir2(μ-Cl)2(η⁴-cod)2] (cod = 1,5-cyclooctadiene) and [Ir2Cl2(μ-Cl)2(η⁵-Cp*)2] (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) at room temperature led to simple coordination of t...

Different coordination modes of a PGeP chloridogermyl ligand (Ge,P-chelating and P,Ge,P-tripodal) and a PGeP germylene ligand (P,Ge,P-bridging and Ge,P-chelating) have been identified in coordination compounds resulting from reactions of the PGeP pincer-type diphosphane-germylene Ge(NCH2PtBu2)2C6H4 (1) with iridium(I), manganese(0), and ruthenium(I...

Reactions of the first-generation Grubbs’ catalyst trans-[RuCl2(CHPh)(PCy3)2] (1) with the amidinatogermylenes Ge(tBu2bzam)R (R = tBu (L¹), CH2SiMe3 (L²); tBu2bzam = N,N′-bis(tertbutyl)benzamidinate) have allowed the isolation and full characterization of the first specimens of Grubbs-type carbene complexes featuring heavier tetrylenes as ancillary...

The non-donor-stabilized PSnP pincer-type stannylene Sn(NCH2PtBu2)2C6H4 (1) has been prepared by treating SnCl2 with Li2(NCH2PtBu2)2C6H4. All attempts to synthesize the analogous PSiP silylene by reduction of the (previously unknown) silanes SiCl2(NCH2PtBu2)2C6H4 (2), SiHCl(NCH2PtBu2)2C6H4 (3) and SiH(HMDS)(NCH2PtBu2)2C6H4 (4: HMDS = N(SiMe3)2) hav...

The PGeP pincer-type germylene Ge(NCH2PtBu2)C6H4 (1) has been used to prepare a family group 10 metal complexes, namely, [MCl{κ3P,Ge,P-GeCl(NCH2PtBu2)2C6H4}] (M = Ni (2Ni), Pd (2Pd), Pt (2Pt)), featuring a chloridogermyl PGeP pincer ligand and a Cl-Ge-M-Cl bond sequence. Their reactivity is not initially centered on the metal atom but on their Ge a...

The borane adduct of the 2-(methylamido)pyridine anion, [mapyBH3](-), has been incorporated into octahedral metal complexes. In fac-[Mn(κ(3)N,H,H-mapyBH3)(CO)3] (1) and fac-[RuH(κ(3)N,H,H-mapyBH3)(CO)(PiPr3)] (2), which have been prepared by treating K[mapyBH3] with fac-[MnBr(MeCN)2(CO)3] and [RuHCl(CO)(PiPr3)2], respectively, it behaves as a tripo...

A PGeP pincer-type germylene, Ge(NCH2P(t)Bu2)2C6H4, which contains two phosphane groups hanging from the N atoms of an N-heterocyclic germylene fragment, has been isolated for the first time. This compound has already furnished a rich transition metal derivative chemistry (Co, Rh, and Pd) that includes complexes containing bridging P,Ge,P-, chelati...

The complexes [M(κ³-N,H,H-mapyBH3)(cod)] (M = Rh, Ir; HmapyBH3 = 2-(methylamino)pyridine-borane; cod = 1,5-cyclooctadiene), which contain a novel anionic tripod ligand coordinated to the metal atom through the amido N atom and through two H atoms of the BH3 group, were prepared by treating the corresponding [M2(μ-Cl)2(cod)2] (M = Rh, Ir) precursor...

The manganese(I) carbonyl complex [MnBr{Ge(Pr-2-bzam)tBu}(CO)(4)] (1;'Pr(2)bzam 1,3-di(isopropyl)benzamidinate); which contains an amidinatogermylene ligand, reacts with LiPh or LitBu at room temperature undergoing a reductive dimerization process that leads to the manganese(0) dinier [Mu(2){Ge(Pr(2)bzam)tBu}(2)(CO)(8)]. This complex arid' the mono...

The amidinatogermylene-bridged diruthenium(0) complex [Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)7] (2; (i)Pr2bzam = N,N'-bis(iso-propyl)benzamidinate; HMDS = N(SiMe3)2) reacted at room temperature with (t)BuNC and PMe3 to give [Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(L)(CO)6] (L = (t)BuNC, 3; PMe3, 4), which contain the new ligand in an axial position...

The reactivity of ruthenium carbonyl with amidinatogermylenes of the type Ge(R2bzam)(t)Bu (R2bzam = N,N'-disubstituted benzamidinate) was studied for R = (t)Bu (1tBu) and (i)Pr (1iPr). The mono-, bi-, and/or trinuclear derivatives [Ru(1R)(CO)4], [Ru(1R)2(CO)3], [Ru2(1iPr)(CO)7], [Ru3(1tBu)(CO)11], [Ru3(1tBu)2(CO)10], and [Ru3(1R)3(CO)9] (R = (t)Bu,...

The unprecedented transformation of a terminal two-electron-donor amidinate-germylene ligand into a chelating three-electron-donor κ(2)-N,Ge-imine-germanate ligand has been achieved by treating the manganese amidinate-germylene complex [MnBr{Ge((i)Pr2bzam)(t)Bu}(CO)4] (1; (i)Pr2bzam = N,N'-bis(isopropyl)benzamidinate) with LiMe or Ag[BF4]. In these...

The reactions of [Co2(CO)8] with one equiv of the benzamidinate (R2bzam) group-14 tetrylenes [M(R2bzam)(HMDS)] (HMDS = N(SiMe3 )2 ; 1: M = Ge, R = iPr; 2: M = Si, R = tBu; 3: M = Ge, R = tBu) at 20 °C led to the monosubstituted complexes [Co2{κ(1)M-M(R2bzam)(HMDS)}(CO)7] (4: M = Ge, R = iPr; 5: M = Si, R = tBu; 6: M = Ge, R = tBu), which contain a...

The ruthenium(0) complex [Ru{κ2C2-MeIm(CH2)3ImMe}(CO)3] (1), MeIm(CH2)3ImMe = 1,3-bis(3-methylimidazol-2-yliden-1-yl)propane, which contains a chelating bis(N-heterocyclic carbene) ligand, reacts with MeOTf at room temperature to give the ionic ruthenium(II) methyl derivative [RuMe{κ2C2-MeIm(CH2)3ImMe}(CO)3]OTf ([2]OTf), whereas an analogous reacti...

The C-alkyl groups of cationic triruthenium cluster complexes of the type [Ru3 (μ-H)(μ-κ(2) N(1) ,C(2) -L)(CO)10 ](+) (HL represents a generic C-alkyl-N-methylpyrazium species) have been deprotonated to give kinetic products that contain unprecedented C-alkylidene derivatives and maintain the original edge-bridged decacarbonyl structure. When the s...

The high basicity of a trimethylene-linked bis(NHC), acting as a chelating ligand in a ruthenium(0) complex, is responsible for its involvement in a room-temperature reaction in which the metal atom to which this bis(NHC) ligand is coordinated replaces a hydride anion of the ligand trimethylene linker, which can be taken by a hydride abstractor as...

The methylation of the uncoordinated nitrogen atom of the cyclometalated triruthenium cluster complexes [Ru(3) (μ-H)(μ-κ(2) N(1) ,C(6) -2-Mepyr)(CO)(10) ] (1; 2-MepyrH=2-methylpyrimidine) and [Ru(3) (μ-H)(μ-κ(2) N(1) ,C(6) -4-Mepyr)(CO)(10) ] (9; 4-MepyrH=4-methylpyrimidine) gives two similar cationic complexes, [Ru(3) (μ-H)(μ-κ(2) N(1) ,C(6) -2,3-...

The C‐alkyl groups of cationic triruthenium cluster complexes of the type [Ru3(μ‐H)(μ‐κ2N 1,C2 ‐L)(CO)10]+ (HL represents a generic C‐alkyl‐N‐methylpyrazium species) have been deprotonated to give kinetic products that contain unprecedented C‐alkylidene derivatives and maintain the original edge‐bridged decacarbonyl structure. When the starting com...

The bis(N-heterocyclic carbene) 1,1′-dimethyl-3,3′-(o-xylylene)diimidazol-2,2′-diylidene (MeImCH2C6H4CH2ImMe) reacted with [Ru3(CO)12] at room temperature, in a 3/1 molar ratio, to give the mononuclear derivative [Ru(κ2C2-MeImCH2C6H4CH2ImMe)(CO)3] (1), which contains a chelating bis(NHC) ligand. However, the use of a 1/1 ratio of the reactants led...

The quinoline-functionalized N-heterocyclic carbene 1-(8-quinolyl)methyl-3-methylimidazol-2-ylidene (QuinCH2ImMe) reacted with [Ru3(CO)12] at room temperature to give the monosubstituted derivative [Ru3(κCNHC-QuinCH2ImMe)(CO)11] (1), which, upon heating in refluxing THF, underwent a thermally induced double C(sp3)–H bond activation to give the dihy...

The C-alkyl groups of C-alkylpyrazinium-derived ligands have been selectively deprotonated by K[N(SiMe(3))(2)], through charge-controlled processes, to give neutral products that contain C-alkylidenepyrazine-derived ligands.

The reaction of [Ru(3)(CO)(12)] with pyrimidine (Hpym) leads to the isomeric cyclometalated derivatives [Ru(3)(mu-H)(mu-kappa(2)N(1),C(6)-pym)(CO)(10)] (1) and [Ru(3)(mu-H)(mu-kappa(2)N(1),C(2)-pym)(CO)(10)] (2), which have been treated with [Me(3)O][BF(4)] to give the corresponding N-methylpyrimidinium derivatives [Ru(3)(mu-H)(mu-kappa(2)N(1),C(6)...

The trinuclear cluster [Ru-3(CO)(12)] reacts at room temperature with the phosphine-functionalized N-heterocyclic carbene (NHC) ligand 1[2-(diphenylphophino)ethyl]-3-methylimidazol-2-ylidene (dppeImMe), in 1:1 mol ratio, to give the edge-bridged trinuclear derivative [Ru-3(mu-kappa C-2,P-dppeImMe)(CO)(10)] (1). The use of a 1:3 [Ru-3(CO)(12)] to dp...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Terminal allenes, H(2)CCCR(1)R(2) (R(1) = R(2) = Me; R(1) =SiMe(3), R(2) = Me; R(1) = CO(2)Et, R(2) = H; R(1) =Cy, R(2) = H, react with the hydrazido-capped hydrido carbonyl triruthenium complex [Ru(3)(mu-H)(mu(3)-kappa(2)-HNNMe(2))(CO)(9)] (1) in THF at reflux temperature to give the allyl-bridged derivatives [Ru(3)(mu-H)(mu(3)-kappa(3)-H(2)CCHCR(...

Six-membered-ring N-heterocyclic carbenes having only one N atom (NHC1N-R6 carbenes) can be easily prepared by simple deprotonation of readily available N-methylpyridinium-type cations with K[N(SiMe3)(2)]. They have been trapped in solution with [Ru-3(CO)(12)] to give novel triruthenium clusters that contain orthometalated NHC1N-R6 carbene ligands...

Ylides derived from 2-acylmethyltriazolopyridinium salts (2a) -(2c) react with methyl or ethyl propiolate and with dimèthyl acetylenedicarboxylate to give ylides (3a)–(3e), (6) or (7). In some cases 1:2 adducts are formed, shown to be the novel ylides (8a)–(8d); an X-ray diffraction confirms structure (8a).

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

A DFT computational study on the reaction that transforms the triruthenium cluster [Ru3(μ3-κ2-HNNMe2)(μ3-κ2-HCCH2)(μ-κ2-HCCH)(CO)7] (1), which contains an edge-bridging acetylene ligand, into the derivative [Ru3(μ3-κ2-HNNMe2)(μ3-κ2-HCCH2)(μ-κ1-CCH2)(CO)7] (2), which contains an edge-bridging vinylidene ligand, is reported. The reaction pathway with...

The unsaturated triosmium dihydrido cluster [Os3(μ-H)2(CO)10] (1) reacts at room temperature with N-heterocyclic carbenes (NHCs) of the 1,3-disubstituted imidazol-2-ylidene type (R1R2Im). While the addition product [Os3H(μ-H)(NHC)(CO)10] has been obtained only for NHC = Mes2Im, CO-substitution derivatives of the type [Os3(μ-H)2(NHC)(CO)9] have been...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The cationic cluster complexes [Ru(3)(mu-H)(mu-kappa(2)N,C-L(1) Me)(CO)(10)](+) (1(+); HL(1) Me=N-methylpyrazinium), [Ru(3)(mu-H)(mu-kappa(2)N,C-L(2) Me)(CO)(10)](+) (2(+); HL(2) Me=N-methylquinoxalinium), and [Ru(3)(mu-H)(mu-kappa(2)-N,C-L(3) Me)(CO)(10)](+) (3(+); HL(3) Me=N-methyl-1,5-naphthyridinium), which contain cationic N-heterocyclic ligan...

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

{Terminal allenes, (H2CCCRR2)-R-1 (R-1 = R-2 = Me; R-1 =SiMe3

Density functional theory calculations on the reaction that gives the edge-bridging allyl cluster [Ru(3)(mu-kappa(3)-C(6)H(9)) (mu(3)-kappa(2)-HNNMe(2))(mu-CO)(2)(CO)(6)] from [Ru(3)(mu-H)(mu(3)-kappa(2)-HNNMe(2))(CO)(9)] and cyclohexa-1,3-diene have shown that this reaction follows a three-step process. The first step, which is rate-limiting and i...

The cationic cluster complexes [Ru3(CO)10(mu-H)(mu-kappa2N,C-L1Me)]+ (3+; HL1=quinoxaline) and [Ru3(CO)10(mu-H)(mu-kappa2N,C-L2Me)]+ (5+; HL2=pyrazine) have been prepared as triflate salts by treatment of their neutral precursors [Ru3(CO)10(mu-H)(mu-kappa2N,C-Ln)] with methyl triflate. The cationic character of their heterocyclic ligands is respons...

The tetraruthenium tetrahydrido cluster compound [Ru-4(mu-H)(4)(CO)(12)] (1) reacts at room temperature with N-heterocyclic carbenes of the 1,3-disubstituted imidazolin-2-ylidene type (R(1)R(2)Im) to give the carbonyl substitution products [Ru-4(mu-H)(4)(CO)(11)(R(1)R(2)Im)] ((RRIM)-R-1-I-2 = 1,3-dimethylimidazolin-2-ylidene, 2; 1-phenyl-3-methylim...

(Chemical Equation Presented) Pyrid-2-ylidenes are trapped in solution by [Ru3(CO)12] after being formed by deprotonation of N-substituted pyridinium cations. The great basicity of these NHC ligands and the polynuclear character of the ruthenium cluster trigger room temperature orthometalation of the initial κ1-C2-pyrid-2-ylidene ligands, leading t...

Pyrid-2-ylidene können abgefangen werden, wenn sie in Lösung durch Deprotonierung von N-substituierten Pyridiniumionen in Gegenwart von [Ru3(CO)12] erzeugt werden. Die starke Basizität der NHC-Liganden und die Bindung an den Rutheniumcluster begünstigen eine Orthometallierung, die den ursprünglich gebildeten κ1-C 2-Pyrid-2-yliden-Liganden bei Raumt...

The mechanisms of two recently reported thermal transformations of NHC-triruthenium and -triosmium cluster complexes, which involve the unusual oxidative addition of two C-H bonds of an NHC N-methyl group, have been investigated by density functional theory calculations. The transformations of [M-3(Me(2)Im)(CO)(11)] (Me2IM = 1,3-dimethylimidazol-2-...

The thermolysis of the NHC triosmium cluster [Os3(Me2Im)(CO)11] (1a; Me2Im = 1,3-dimethylimidazol-2-ylidene) in toluene at reflux temperature sequentially affords the edge-bridged cluster [Os3(micro-H)(micro-kappa2-MeImCH2)(CO)10] () and the face-capped derivative [Os3(micro-H)2(micro3-kappa2-MeImCH)(CO)9] (3a). These products result from the seque...

The reactions of the hydrido triruthenium complex [Ru-3(mu-H)(mu(3)-kappa(2)-HNNMe2)(CO)(9)] (1; H2NNMe2 = 1, 1-dimethylhydrazine) with conjugated dienes give trinuclear derivatives that contain edge-bridging allyl ligands. The isolated allyl products are [Ru-3(mu-k(2)-C8H13)(mu(3)-k(2)-HNNMe2)(mu-CO)(2)(CO)(6)] (2) from 1,3-cyclohetadiene, [Ru-3(m...

The room-temperature reactions of [Ru-3(CO)(12)] and [Os-3(CO)(12)] with a variety of N-heterocyclic carbenes (NHCs) have been studied. [Ru-3(CO)(12)] reacts easily with N,N'-dimethylimidazol-2-ylidene (Me(2)Im), more slowly with N-methyloxazol-2-ylidene (MeOx), and very slowly with N,N'-dimesitylimidazol-2-ylidene (Mes(2)Im) to give the correspond...

The cluster [Ru3(μ3-κ2-HNNMe2)(μ-κ2-PhCHCPh)(μ-CO)2(CO)6], which has a face-capping 1,1-dimethylhydrazido and an edge-bridging 1,2-diphenylethenyl ligand, reacts with diphenylbutadiyne or 2,4-hexadiyne to give the isomeric triruthenium carbonyl cluster complexes [Ru3(μ3-κ2-HNNMe2)(μ-κ2-PhCHCPh){μ3-κ4-RCCCC(R)C(R)CCCR}(CO)6] (3a, R=Ph; 3b, R=Me) and...

Complexes [Ru(η5-C5H5){κ3(P,C,C)-Ph2P(CH2)nCHCH2}(MeCN)][PF6] (n = 1 (1), 2 (2)) react with CC bonds of propargylic alcohols to yield regioselectively the complexes [Ru(η5-C5H5){κ(P),η4-Ph2P(CH2)nCHCHC(R)CH2}][PF6] (n = 1, R = CPh2OH (3), C(C12H8)OH (4), C(C4H8)OH (5), CMePhOH (6a, 6b); n = 2, R = CPh2OH (7), C(C4H8)OH (8), CMePhOH (9a, 9b), CHPhOH...

The reactions of doubly face-capped triruthenium cluster complexes of the type [Ru(3)(mu(3)-kappa(2)-HNNMe(2))(mu(3)-kappa(2)-R(2)CCHR(1))(mu-CO)(2)(CO)(6)] (HNNMe(2) = 1,1-dimethylhydrazide; R(2)CCHR(1) = alkenyl ligand) with terminal and internal alkynes have been studied in refluxing toluene. The following derivatives have been isolated from the...

The reactions of the hydrido-triruthenium cluster complex [Ru3(mu-H)(mu3-kappa(2)-HNNMe2)(CO)9] (1; H2NNMe2 = 1,1-dimethylhydrazine) with alkynes that have alpha-hydrogen atoms give trinuclear derivatives containing edge-bridging allyl or face-capping alkenyl ligands. Under mild conditions (THF, 70 degrees C) the isolated products are as follows: [...

Los objetivos generales de la asignatura Experimentación en Química Física son: aprender a organizar un cuaderno de laboratorio, estructurar y analizar la información generada en el laboratorio de forma científicamente correcta, comprender el funcionamiento del instrumental utilizado y comprender y saber manejar los conceptos y cálculos realizados...

EHMO calculations have revealed that alkynes bridging four metal atoms are four-electron-donor ligands and that alkenyl groups bridging three metal atoms are three-electron-donor ligands. Therefore, the answer to the title question is "no". The clusters that contain these ligands have large HOMO-LUMO gaps, despite being electronically unsaturated (...

The reactions of the 1,1-dimethylhydrazine-derived cluster [Ru-3(mu-H)(mu(3)-eta(2)-HNNMe2)(CO)(9)] with conjugated diynes, RC4R (R = Me, Ph), afford the ynenyl derivatives [Ru-3(mu(3)-eta(2)-HNNMe2)(mu(3)-eta(2)-RCCCCHR)(mu-CO)(2)(CO)(6)] (R = Me) and [Ru-3(mu(3)-eta(2)-HNNMe2)(mu(3)-eta(2)-RCCCCHR)(mu-CO)(CO)(7)] (R = Me, Ph), featuring eta(2)-ed...

The reactions of the 1,1-dimethylhydrazine-derived cluster [Ru-3(mu-H)(mu(3)-eta(2)-HNNMe2)(CO)(9)] with conjugated diynes, RC4R (R = Me, Ph), afford the ynenyl derivatives [Ru-3(mu(3)-eta(2)-HNNMe2)(mu(3)-eta(2)-RCCCCHR)(mu-CO)(2)(CO)(6)] (R = Me) and [Ru-3(mu(3)-eta(2)-HNNMe2)(mu(3)-eta(2)-RCCCCHR)(mu-CO)(CO)(7)] (R = Me, Ph), featuring eta(2)-ed...

The reactions of the triruthenium cluster complex [Ru3(μ-H)(μ3-η2-HNNMe2)(CO)9] (1; H2NNMe2=1,1-dimethylhydrazine) with alkynes (PhCCPh, HCCH, MeO2CCCCO2Me, PhCCH, MeO2CCCH, HOMe2CCCH, 2-pyCCH) give trinuclear complexes containing edge-bridging and/or face-capping alkenyl ligands. Whereas the edge-bridged products are closed triangular species (thr...

The reaction of the cluster complex [Ru-3(mu-H)(mu(3)-eta(2)-apyr)(CO)(9)] (1; Hapyr = 2-aminopyrimidine) with 1,6-diphenoxy-2,4-hexadiyne in refluxing THF gives the trinuclear derivative [Ru-3(mu(3)-eta(2)-apyr)(mu-eta(3)-PhOCH2CH=CCdropCCH(2)OPh)(mu-CO)(2)(CO)(6)] (2), which contains an edge-bridging ynenyl ligand. Heating 2 in refluxing toluene...

The oxo-bridged dinuclear complexes [(μ-O){ReOCl2(L)}2] [L = 2-(1-ethylaminomethyl)-1-methylimidazole (eami); 2-(1-methylaminomethyl)-1-methylimidazole (mami); 2-(1-ethylthiomethyl)-1-methylimidazole (etmi)] were prepared by reaction of trans-[ReOCl3(PPh3)2] with L in acetone. X-ray crystallographic studies of the eami and etmi complexes show that...

Reaction of LiC9H7 with [OsBr2(PPh3)3] gives the complex [Os(η5-C9H7)Br(PPh3)2] (1). The analogous complex [Os(η5-C9H7)I(PPh3)2] (2) is obtained from the metathesis reaction of [Os(η5-C9H7)Cl(PPh3)2] with NaI. The treatment of [Os(η5-C9H7)X(PPh3)2] with NaOMe leads to the hydride derivative [Os(η5-C9H7)H(PPh3)2] (3) which can be protonated with HBF...

The diphenylallenylidene complex [Ru(=C=C=CPh2)(eta(5)-C9H7)(PPh3)(2)][PF6] (1) regioselectively reacts at the C-gamma atom with the lithium enolate derived from (1R)-(+)-camphor to yield sigma-alkynyl derivative [Ru{CdropCCPh(2)(C10H15O)}(n(5)-C9H7)(PPh3)(2)] (2). Complex 2 was obtained as a non-separable mixture of two diastereoisomers, i.e. (1R,...

A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl]2*CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C(ipso) atom of the arene lies almost at the fourth plan...

A series of dichloro-bridged arylbicycloheptylpalladium complexes have been synthesized and characterized by means of NMR spectroscopy. The compound [(C16H19)PdCl](2).CH2Cl2 with ortho and para methyl substituents at the arene has been characterized by means of X-ray diffraction techniques. The C-ipso atom of the arene lies almost at the fourth pla...

The compound [Ru3(CO)9[mu-P(NPri2)2]3][Ru6(CO)15(mu 6-C)[mu-P(NPri2)2]] (1), obtained via the addition of PCl(NPri2)2 to K2[Ru4(CO)13], crystallizes in the monoclinic space group P2l/c with a = 15.537(8) A, b = 36.151(16) A, c = 19.407(5) A, beta = 91.14(2) degrees, Z = 4, and R = 0.069 for 8006 observed reflections. The unit cell is unusual in tha...

A review of all of the known structural stereotypes of dimeric Pt(I) or Pd(I) systems with at least one bridging phosphido group is presented. The nature of the direct metal-metal interaction is affected by the number, nature, and disposition of the various coligands. It appears that in some cases a bent M-M bond is by itself a center of nucleophil...

The transformation of acetylene into vinylidene, as promoted by the metal fragment [(pp3)Co]+ [pp3 = P(CH2CH2PPh2)3], is unimolecular and features the hydride–acetylide species as an intermediate. The paper describes a detailed ab initio study of the reaction, in particular with regard to the step involving 1,3-H shift. The best computational resul...

Heating under reflux solutions of the monosubstituted vinylidene complex [Ru{CC(H)Ph}(η5-C9H7)(PPh3)2][PF6] (1) in nitriles yields the complexes [Ru(NCR)(η5-C9H7)(PPh3)2][PF6] (R = Me (2a), Et (2b), Ph (2c)) and phenylacetylene. The process proceeds via an initial η1-vinylidene-η2-alkyne tautomerization followed by the displacement of the coordinat...

The dinuclear cyclopalladated compounds [Pd(μ-Cl)Ln]2 (2) [HLn = p-CnH2n+1OC6H4CH=NC 6H4OCnH2n+1-p (n = 6, 8, and 10)] react with silver thiolates AgSRm (Rm = CmH2m+1, m = 6, 8, 10, and 18) to give dinuclear derivatives with mixed bridges [Pd2(μ-Cl)(μ-SRm)Ln2] (3). Treatment of derivatives 2 with silver acetate (Pd/AgOAc = 2:1) or treatment of [Pd(...

The dinuclear cyclopalladated compounds [Pd(μ-Cl)Ln]2(2) [HLn = p-CnH2n+1OC6H4CH=NC6H4OCnH2n+1-p (n = 6, 8, and 10)] react with silver thiolates AgSRm (Rm = CmH2m+1, m = 6, 8, 10, and 18) to give dinuclear derivatives with mixed bridges [Pd2(μ-Cl)(μ-SRm)Ln2] (3). Treatment of derivatives 2 with silver acetate (Pd/AgOAc = 2:1) or treatment of [Pd(μ-...

New consideration of the chemical bonding in [L3M(μ-P3)M′L3]n+ complexes (triple-deckers with bifacial coordination of the unit P3) focuses on the active role played by the P3 σ bonding network. The argument, developed from an extended Hückel molecular orbital (EHMO) analysis, is based largely on the rigorous symmetry properties of the MO interacti...

The structure of lithiated P-diphenyl(methyl) (N-phenyl)phosphazene (Li(+)1a(-)) has been determined. The crystal structure consists of monomeric units containing a four-membered ring with the lithium bonded to the nitrogen and methylene carbon atoms of the phosphazene. The coordination sphere of the metal is completed by two molecules of THF. The...

The sigma-alkynyl complexes [Ru(C=CR1)(eta5-C9H7)L2] (L2 = 2PPh3, 1,2-bis(diphenylphosphino)ethane (dppe), R1 = Ph, (t)Bu, (n)Pr; L2 = bis(diphenylphosphino)methane (dppm), R1 = Ph) have been prepared by reaction of the complex [RuCl(eta5-C9H7)L2] with HC=CR1 and potassium hydroxide in refluxing methanol. Electrophilic additions of HBF4.OEt2 and Me...

The structure and absolute configuration of the title compound, [W(CO)5(C20H32O4Si)], is reported. The W atom has distorted octahedral coordination defined by one carbene and five carbonyl ligands.

Rh2(O2CCF3)3[(C6H4)PPh2]·(HO2CCF3)2 reacts with PPh3 yielding the doubly metalated compound Rh2(O2CCH3)2− [(C6H4)PPh2]2·(HO2CCF3)2. The reaction proceeds via a reactive intermediate with an equatorial phosphine, Rh2(η2-O2CCF3)(μ-O2CCF3)2[(C6H4)PPh2](PPh3)·(HO2CCF3), which can also be generated in moderate yield under photochemical conditions. The s...

The σ-alkynyl complexes [Ru(C≡CR1)(η5-C9H7)L 2] (L2 = 2PPh3, 1,2-bis(diphenylphosphino)ethane (dppe), R1 = Ph, tBu, nPr; L2 = bis(diphenylphosphino)methane (dppm), R1 = Ph) have been prepared by reaction of the complex [RuCl(η5-C9H7)L2] with HC≡CR1 and potassium hydroxide in refluxing methanol. Electrophilic additions of HBF4·OEt2 and MeOSO2CF3 to...

X-Ray structural studies on the redox pair trans-[Mn(CN)(CO)(dppm)2](dppm = Ph2PCH2PPh2) and trans-[Mn(CN)(CO)(dppm)2][PF6]·CH2Cl2 showed that one-electron oxidation results in changes consistent with depopulation of an orbital involved in Mn–P π-back bonding. The ESR spectra of trans-[Mn(CN)(CO)(dppm)2]+, [Mn(CO)(CNCH2CHCH2)(dppm)2]2+, trans-[Mn(C...

The crystal structure of the Zn(sulfathiazole)2·H2O complex is reported. The complex crystallizes in the monoclinic space group C2/c. The cell dimensions are a = 9.098(3) Å, b = 17.871(5) Å, c = 14.61(1) Å, β = 99.44(6)°, V = 2343(2) Å3, Z = 4, and Dx = 1.68 g/cm3. The final conventional R-factor = 0.027 for 2669 “observed” reflections and 191 vari...

Molecular orbital calculations at the extended Huckel level have been carried out on the model binuclear cyano-bridged cationic complexes of the type {[Mn]-CN-[Mn]}+ where [Mn] = cis- or trans-mer-Mn(CO)2(PH3)3+. The results are consistent with a weak Mn- - -Mn interaction mediated by the CN bridge. The energy and composition of the highest occupie...

The synthesis of mono- and trihalogenated derivatives of 2-aza 1,3-dienes 2 and 3 is described. The first example of diastereofacial selectivity in Diels-Alder reactions of heterodienes of type 2 with electron-poor dienophiles is reported, and a model for the explanation of the observed epimeric ratios, based on the interactions between diene and d...

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In order to complete the study of the reactivity of 5-membered heterocycles, compound (I) is treated with (II).