X-ray structures of cobalt(III) complexes with bio-relevant pyrazolyl thiosemicarbazone: Indication of structural changes on the increasing bulkiness of the alkyl substituents on thiosemicarbazone moiety

X-ray crystallographic studies of cobalt(III) complexes of 5-methyl-3-formylpyrazole-N(4)-diethylthiosemicarbazone (HMP_zNEt₂), [Co(MP _z NEt ₂ ) ₂ ]Br·2H ₂ O, 5-methyl-3-formylpyrazole-N(4)-dipropylthiosemicarbazone (HMP_zNPr ₂ ), [Co(MP _z NPr ₂ ) ₂ ]Br·2H ₂ O and 5-methyl-3formylpyrazole-N(4)-dibutylthiosemicarbazone (HMP_zNBu ₂ ), [Co(MP _z NBu ₂ ) ₂ ]Br·H ₂ O, have been reported. In all the three complex species, X-ray crystallography has authenticated a CoN₄S₂ octahedral coordination with the pair of orthogonally coordinated NNS tridentate ligands in the monodeprotonated form of the ligand. The two azomethine nitrogen atoms are trans to each other, while the pyrazolyl ring nitrogens and the thiolato sulfurs are in cis positions. A gradual decrease in the dihedral angle between the coordinating ligands has been observed with increase in the bulkiness of the aliphatic side chains of the substituent on the thiosemicarbazone moieties. In all the three complexes, intraligand C–H···S contacts appear to arrest the free rotation of the side chains about the C(6)–N(5) single bond. ^†Deceased     

Polymerizations of methyl methacrylate and rac-lactide by zinc(II) precatalyst containing N-substituted 2-iminomethylpyridine and 2-iminomethylquinoline

The reaction of [ZnCl₂] with N-cyclopentyl-1-(quinolin-2-yl)methanimine (L_A), N-cyclohexyl-1-(quinolin-2-yl)methanimine (L_B), N-cyclohexyl-1-(pyridin-2-yl)methanimine (L_C), 2,6-diethyl-N-(pyridin-2-ylmethylene)aniline (L_D), N-cyclopentyl-1-(pyridin-2-yl)methanimine (L_E), and N-phenyl-(pyridin-2-yl)methanimine (L_F) in ethanol produced the bidentate [(NN′)ZnCl₂] complexes, [L_AZnCl₂], [L_BZnCl₂], [L_CZnCl₂], [L_DZnCl₂], [L_EZnCl₂] and [L_FZnCl₂], respectively. The molecular structures revealed that the zinc in [L_nZnCl₂] (L_n = L_A ? L_D) showed a distorted tetrahedral geometry involving two nitrogens of N,N’-bidentate ligands and two chloride ligands. Most of these initiators were effective for polymerization of methyl methacrylate (MMA) and polymerization of rac-lactide (rac-LA). [L_CZnCl₂] (with N-cyclohexyl substituted at imine-pyridine moiety) exhibited the highest catalytic activity for MMA polymerization in the presence of modified methylaluminoxane (MMAO) with an activity of 3.33 × 10⁴ g PMMA/mol·Zn·h at 60 °C, giving moderate syndiotactic poly methyl methacrylate (PMMA) with high molecular weight (9.62 × 10⁵ g/mol). The dimethyl derivatives [L_nZnMe₂] (L_n = L_A ? L_F), generated in situ, polymerized rac-LA with moderate activity and yielded a polylactide (PLA) with good number-average molecular weights and narrower polydispersity indices (PDIs). [L_AZnMe₂] effectively initiates the ring-opening polymerization (ROP) of rac-LA to attain heterotactic PLA (P_r = 0.91).     

Synthesis,Characterization, and Structure of Metal(II) (-)-Sparteine Complexes Containing Acetate Ligands

The complexes [Co(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (1), [Ni(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (2), [Cu(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (3) and [Zn(C₁₅H₂₆N₂)(C₂H₃O₂)₂] (4) were prepared from reaction of (?)-sparteine with the corresponding metal(II) acetates in ethanol at stoichiometric ligand to metal ratios. The complexes were characterized by UV-Vis and IR spectroscopies, and magnetic susceptibility measurements. The solid-state structures of 1, 2 and 4 have been determined by X-ray crystallography. The Complexes 1 and 2 display a pseudo-octahedral structure around the metal center, where two acetate ligands coordinate to the metal center in a bidentate fashion, whereas the metal centers in 3 and 4 adopt a pseudo-tetrahedral structure and two acetate ligands in these complexes coordinate to the metal center in a monodentate fashion. The whole set of prepared complexes has been used for comparative structural and spectroscopic studies.     

Titanium-Substituted Heteropolytungstates as Model Catalysts for Studying the Mechanisms of Selective Oxidation by Hydrogen Peroxide

The ³¹P NMR method shows that four forms of titanium(IV)-monosubstituted Keggin-type heteropolytungstate (Ti–HPA) exist in MeCN: the dimer (Bu₄N)₇[{PTiW₁₁O₃₉}₂OH] (in the abbreviated form, (PW₁₁Ti)₂OH or H1), its conjugate base (PW₁₁Ti)₂O (1), and two monomers, PW₁₁TiO (2) and PW₁₁TiOH (H2). The ratio between the forms depends on the concentrations of H⁺and H₂O. Dimer H1is produced from 2in MeCN when H⁺(1.5 mol) is added, and monomer H2is the key intermediate in this process. The catalytic activity of Ti–HPA in the oxidation of thioethers by H₂O₂correlates with their activity in peroxo complex formation and decreases in the order H2> H1> 2. The reaction of 2with H₂O₂in MeCN occurs slowly to form the inactive peroxo complex PW₁₁TiO₂(A). The addition of H₂O₂to H1and H2most likely results in the formation of the active hydroperoxo complex PW₁₁TiOOH (B). Complexes Aand Btransform into each other when H⁺or OH^–(1 mol) is added per 1 mol of Aor B, respectively. The activity of Btoward thioethers in the stoichiometric reaction is proven by ³¹PNMR and optical spectroscopy.     

Self-Assembly of Supramolecular Architectures Using Chlorotetra(Pyrrole-2-Carboxylato)Diruthenium Molecules as Building Blocks

Two new complexes, based on the unit Ru₂Cl(μ-O₂CC₄H₄N)₄ (1) (O₂CC₄H₄N = pyrrole-2-carboxylate), Ru₂Cl(μ-O₂CC₄H₄N)₄(H₂O)·4H₂O [1(H ₂ O)·4H ₂ O], and Ru₂Cl(μ-O₂CC₄H₄N)₄(Me₂CO) [1(Me ₂ CO)], are synthesized and structurally characterized. The physical properties of these complexes are studied and compared with those previously reported for Ru₂Cl(μ-O₂CC₄H₄N)₄(thf)·thf·H₂O [1(thf)·thf·H ₂ O]. The nature of the solvent molecule bonded to the axial position of the dimetallic unit determines the supramolecular interactions leading to different arrangements in the solid state. The presence of NH groups in the pyrrolic rings favours the existence of hydrogen bond interactions that are present in the three complexes. In addition, complex 1(Me ₂ CO) shows π–π stacking interactions through pyrrolic rings of different dimetallic units. Dedicated to the memory of Prof. F. Albert Cotton.     

Electronic states of XC<Subscript>3</Subscript>H<Subscript>3</Subscript>Si five-membered rings (X = CH,N, P,and As)

Stable configurations of XC₃H₃Si five-membered rings, 1 _X and 2 _X (X = CH, N, P, and As) in the singlet and triplet states are found at B3LYP/6-311++G** level of theory. All the singlet states of 1 _X and 2 _X have lower potential energy than the triplet state. The ΔG _s−t differences between the singlet and triplet states of 1 _X and 2 _X changes at the B3LYP/6-311++G** level in the order (in kcal/mol): 1 _N (−17.56) > 1 _CH (−15.26) > 1 _P (−4.96) > 1 _As (−3.45) and 2 _CH (−15.26) > 2 _N (−9.21) > 2 _P (−7.39) > 2 _As (−6.15), respectively.     

SYNTHESIS OF NEW 3-SUBSTITUTED AND SPIRO 1,5-BENZODIAZEPIN-2-ONES UNDER PHASE-TRANSFER CATALYSIS CONDITIONS

1,3-Dihydro-4-phenyl-1,5-benzodiazepin-2-one 1 was treated with bromine in 1:1 molar ratio to get the corresponding 3-bromo derivative 2 which in turn reacted with different nucleophiles to get the corresponding 3-substituted derivatives 3–11. The cyclized compounds 4_a , 5_a , 7_a,b , and 9_a–c were achieved on refluxing compounds 4, 5, 6_a,b , or 8 _a–c respectively in diphenyl ether. Compound 1 was benzoylated with benzoyl chloride to give the corresponding 1-benzoyl derivative 12 which reacted with bromine in 1:2 molar ratio to yield the corresponding 3,3-dibromo derivative 13. Spiro benzodiazepines 14_a–d–16 were obtained by reacting compound 13 with the proper bidentates. Compound 1 was treated with formaldehyde and secondary amines or thiols to give Mannich bases or sulphides 17–21, respectively.     

Lutetium complexes with tetraphenylethylene dianion. Synthesis and structure

The reactions of dipotassium and disodium salts of the tetraphenylethylene dianion with LuCl₃(THF)₃ or CpLuCl₂(THF)₃ yielded the homoleptic ate-complexes [Na(THF)₅][Lu(Ph₂CCPh₂)₂] (1) and [K(THF)₅][Lu(Ph₂CCPh₂)₂] (2) or the heteroleptic complex CpLu(Ph₂CCPh₂)(THF)₂ (4), respectively. Recrystallization of complex 1 from a diglyme—THF mixture afforded [Na(diglyme)₂][Lu(Ph₂CCPh₂)₂](THF)_0,5 (3). Recrystallization of complex 4 from 1,2-dimethoxyethane gave [CpLu(Ph₂CCPh₂)(DME)](DME) (5). The structures of complexes 3 and 5 were established by X-ray diffraction analysis. In both complexes, the unusual η⁶-coordination of the (Ph₂CCPh₂)²⁻ dianion to lutetium is observed. The Lu-C distances vary from 2.441(2) to 2.643(2) Å (3) and from 2.470(3) to 2.763(3) Å (5). In complexes 3 and 5, a redistribution of the C-C bond lengths was observed in the Ph groups coordinated to lutetium. Studies by ¹H, ¹³C, and 2D NMR spectroscopy demonstrated that the η⁶-coordination of the tetraphenylethylene dianion in homoleptic ate-complexes 1 and 2 is retained in a THF solution, whereas the coordination of this dianion in heteroleptic complex 4 changes from η⁶ to η⁴.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2060–2068, October, 2004.     

半夹芯16电子碳硼烷化合物Me4CpCoS2C2B10H10与二茂铁炔酮的反应性

邻位碳硼烷分别与正丁基锂、硫粉和Me₄CpCo(CO)I₂反应合成得到半夹芯16电子碳硼烷化合物Me₄CpCoS₂C₂B₁₀H₁₀ (1)。1与二茂铁炔酮在二氯甲烷中反应得到产物{(Me₄CpCoS₂C₂B₁₀H₁₀)[FcC(O)CHCCHCC(O)Fc]} (2)(Fc=二茂铁基)。2是一个1:2的加成产物,2个二茂铁炔酮分子以头-尾的方式加成到分子1中的1个Co-S键上。1和2分别用红外、核磁、元素分析、质谱和单晶X-射线衍射等表征方法进行了结构表征。     

PLATINUM(II) COMPLEXES OF P(III) CYCLOPHOSPHAMIDE DERIVATIVES

Abstract

The syntheses of the P(III) analogues of cyclophosphamide, isophosphamide and triphosphamide are reported. These compounds (4–6, respectively) polymerize easily at room temperature but are sufficiently stable in solution to react with Cl₂Pt(NCPh)₂, forming cis-Cl₂Pt(4)₂, cis-Cl₂Pt(5)₂ and cis-Cl₂Pt(6)₂ (complexes 9–11, respectively). Complex 10 can also be made by condensing cis-Cl₂Pt[ClPN(CH₂CH₂Cl)CH₂CH₂CHO]₂ with ClCH₂CH₂NH₂, while an alternate route to 9 and 11 is afforded by the condensation of cis-Cl₂Pt[Cl₂PN(CH₂CH₂Cl)₂]₂ with H₂NCH₂CH₂CH₂OH and ClCH₂CH₂NHCH₂CH₂CH₂OH, respectively. Complexes 9–11 exist in two diastereomeric configurations and these can be separated in the cases of 9 and 11 by column chromatography. ³¹P NMR spectral data for the complexes are discussed and the results of NCl antitumor screening are presented.     

Phase equilibria in systems based on Tl4SnSe3 and Tl4SnSe4 ternary compounds

Phase equilibria in the Tl₄SnSe₃-Tl (I), Tl₄SnSe₃-Sn (II), Tl₄SnSe₄-SnSe (III), Tl₄SnSe{ia4}-TlSe (IV), and Tl₄SnSe₃-Tl₄SnSe₄ (V) systems have been studied by differential thermal analysis and power X-ray diffraction. Systems I–V have been found to have eutectic interactions. In systems I and II, width regions of solid solutions based on the ternary compound Tl₄SnSe₃ are formed.     

Three lanthanide complexes with mixed salicylate and 1,10-phenanthroline: syntheses,crystal structures,and luminescent/magnetic properties

Three new lanthanide complexes incorporating salicylate (HSA or SA) and 1,10-phenanthroline (phen), Ln₃(HSA)₅(SA)₂(phen)₃ [Ln = Ho (1) and Er (2)], and Sm₂(HSA)₂(SA)₂(phen)₃ (3), have been synthesized. X-ray structural analysis reveals that 1 and 2 are isostructural with a trinuclear pattern, and 3 exhibits a binuclear structure. Comparison of the structural differences between 1/2 and 3 suggests that the identity of metal plays an important role in construction of such complexes. The magnetic properties of 1 are discussed. Moreover, 2 and 3 are both photoluminescent materials, and their emission properties are closely related to their corresponding Ln^III centers.     

Ruthenium bis(phosphinite) pincer complexes

Resorcinol-based ruthenium bis(phosphinite) complexes were synthesized. Complexes RuCl(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (9) and RuH(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (10) were obtained by cyclometallation of 1,3-(Bu^t ₂PO)₂C₆H₃ with RuCl₂(DMSO)₄ in 2-methoxyethanol in the presence of Hünig’s base. The interconversion of complexes 9 and 10 was studied. The addition of carbon monoxide to complexes 9 and 10 yielded 18e adducts, RuCl(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (11) and RuH(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (12), respectively. In the case of complex 9, this reaction is reversible. Reaction of complex 10 with trifluoroacetic acid resulted in complex Ru(CF₃COO)(CO)[2,6-(Bu^t ₂PO)₂C₆H₃] (13), which reacted with carbon monoxide to give complex Ru(CF₃COO)(CO)₂[2,6-(Bu^t ₂PO)₂C₆H₃] (14). Based on the IR spectral data, the TFA ligand in complexes 13 and 14 is bound in a bi- and monodentate fashion, respectively. The structure of compound 9 was determined by X-ray diffraction analysis.     

Copper(I) bromide complexes of two 15-memberd O2S2-macrocycles with different sulfur-to-sulfur separations: dimer and one-dimensional coordination polymer

Abstract

A comparative study on the exo-coordination-based networking of 15-membered O₂S₂-macrocycle isomers (L¹ and L²) induced by interdonor distances is reported. In copper(I) bromide complexation, the isomer L¹ incorporating a shorter sulfur-to-sulfur separation yielded a discrete dimer complex [(μ-Cu₂Br₂)(L¹)₂] (1) in which two macrocycles are bridged by a Cu₂Br₂ square cluster. While, the reaction of copper(I) bromide with the isomer L² incorporating a longer sulfur-to-sulfur separation afforded a double-stranded one-dimensional (1D) coordination polymer {[(μ₄-Cu₂Br₂)(L²)₂]·CH₂Cl₂}_n (2) as a kinetic product which converted to [(μ₄-Cu₂Br₂)(L²)₂]_n (3) with different 1D connectivity pattern as a thermodynamic product. The results indicate as examples of programmed self-assembly that the proposed interdonor distances and the ligand isomerism play decisive roles cooperatively in the topologies of the supramolecular products via different coordination modes.     

Novel Methods for the Synthesis of 4‐Arylisoquinolinium Perchlorates and 4‐Arylisoquinolin‐1‐ones

2‐Benzylamino‐1‐phenyl‐ethanones 1 were converted to the corresponding isoquinolinium perchlorates 2 in high yields using 70% HClO₄‐FeCl₃ mixture as a cyclization and oxidation reagent. A mild and high yielding method for the oxidation of perchlorates 2 to isoquinolin‐1‐ones 3 involving the treatment of 2 with KOH and K₃[Fe(CN)₆] in THF‐H₂O two‐phase system at room temperature was developed. Compounds 2a–g were shown to be disproportionate to 3 and the corresponding 1,2‐dihydroisoquinoline 4 in the presence of base, which in turn is oxidized by K₃[Fe(CN)₆] to 2.     

Syntheses and structures of three disulfoxide uranyl complexes

Three disulfoxide uranyl complexes [UO₂(DBSOB)(NO₃)₂] _n (1), [UO₂(DBM)₂]₂(DBSOB) (2), and [UO₂(PMBP)₂]₂(DBSOB) (3) (DBSOB = 1,4-di(butylsulfinyl)butane, HDBM = dibenzoylmethane, HPMBP = 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone) were synthesized and characterized. The [UO₂(NO₃)₂] groups are connected by bridging disulfoxide ligands DBSOB to form a 1-D zigzag chain in 1. Two [UO₂(DBM)₂] or [UO₂(PMBP)₂] groups are connected by a bridging DBSOB to form the dimeric structures of 2 or 3, respectively. Complexes 1, 2, and 3 are the first structurally characterized disulfoxide–actinide compounds. Thermal stabilities of 1, 2, and 3 were investigated.     

Synthesis,structure and methyl methacrylate polymerization of cobalt(II), zinc(II) and cadmium(II) complexes with N,N′,N-bidentate versus N,N′,N-tridentate N,N′,N-bis((1H-pyrazol-1-yl)methyl)amines

Mononuclear Co(II), Zn(II) and Cd(II) complexes derived from bidentate or tridentate N,N′,N-bis((1H-pyrazol-1-yl)methyl)amines (L_n = L_A, L_B), where L_A is N,N-bis((1H-pyrazol-1-yl)methyl)-3-methoxypropan-1-amine and L_B is 3-methoxy-N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)propan-1-amine, have been synthesized and characterized. The geometry at Co(II) and Cd(II) for [L_ACoCl₂], [L_BCoCl₂] and [L_BCdBr₂] with N,N′,N-tridentate ligands (L_n = L_A, L_B) can be described as a distorted trigonal bipyramid achieved by coordinative interaction of N_pyrazole, two halides and the nitrogen of amine moiety. However, the molecular structure of four-coordinate [L_AZnCl₂] can be best described as tetrahedral, resulting in an eight-membered chelate ring. [L_ACoCl₂] polymerized methyl methacrylate in the presence of modified methylaluminoxane at 60 °C and resulted in poly(methylmethacrylate) (PMMA) with higher molecular weight and narrower polydispersity index compared to the other synthesized complexes. However, all the synthesized complexes yielded syndiospecific PMMA, characterized using ¹H NMR spectroscopy, with ca. 0.70.     

Syntheses and crystal structures of cobalt and nickel complexes of 2,6-bis(hydroxymethyl)pyridine

2?:?1 (L?:?M) Complexes of 2,6-bis(hydroxymethyl)pyridine (dhmp) with different Co(II) salts [CoCl₂·6H₂O, Co(SCN)₂, Co(NO₃)₂·6H₂O, CoSO₄·7H₂O and Co(OTos)₂·6H₂O] and Ni(II) salts [NiCl₂·6H₂O, Ni(NO₃)₂·6H₂O, NiSO₄·7H₂O and Ni(OTos)₂·6H₂O] have been prepared (1–9) and studied by infrared spectroscopy and X-ray crystallography. Influences on the distortion of the coordination polyhedron, the arrangement of the donor atoms and the packing structure of the complexes were investigated in terms of the different kinds of anions and cations. In the metal chloride Complexes 1 and 2, water of hydration was found, while in Complex 3 the counterion (SCN^–) acts as a ligand. The crystal structures of all complexes, except 3, show N₂O₄ hexacoordinated metal ions; in 3 the coordination environment is N₄O₂. Complex 1 is another exception in containing cobalt(III) instead of cobalt(II) as for the other complexes with cobalt salts. Logically, in Complex 1, one of the dhmp ligands is mono-deprotonated. In the neutral Complexes 2 and 4–9, the basal planes of the octahedra are made up of O donors and N atoms occupy the axial positions. In 1 as well as in 3, two N and two O atoms form the base, but in 1 O, and in 3 N atoms are on the axis of the coordination sphere. Moreover, the nickel Complexes 2, 5, 7 and 9 are more symmetrical in structure than the cobalt Complexes 1, 4, 6 and 8, in accordance with the Jahn–Teller effect. Packing structures of the complexes show specific interactions based on strong and weak H-bonds that involve the counterions, hydroxy groups and aromatic units, leading to extended network structures.     

Aqua substitution from mononuclear Pt(II) complexes with 2-(pyrazol-1-ylmethyl)quinoline non-leaving ligands

The rates of aqua substitution from [Pt{2-(pyrazol-1-ylmethyl)quinoline}(H₂O)₂](ClO₄)₂, [Pt(H₂Qn)], [Pt{2-(3,5-dimethylpyrazol-1-ylmethyl)quinoline}(H₂O)₂](ClO₄)₂, [Pt(dCH₃Qn)], [Pt{2-[(3,5-bis(trifluoromethyl)pyrazol-1-ylmethyl]quinoline}(H₂O)₂](ClO₄)₂, [Pt(dCF₃Qn)], and [Pt{2-[(3,5-bis(trifluoromethyl)pyrazol-1-ylmethyl]pyridine}(H₂O)₂](ClO₄)₂, [Pt(dCF₃Py)], with three sulfur donor nucleophiles were studied. The reactions were followed under pseudo-first-order conditions as a function of nucleophile concentration and temperature using a stopped-flow analyzer and UV/visible spectrophotometry. The substitution reactions proceeded sequentially. The second-order rate constants for substituting the aqua ligands in the first substitution step increased in the order Pt(dCH₃Qn) < Pt(dCF₃Qn) < Pt(H₂Qn) < Pt(dCF₃Py), while that of the second substitution step was Pt(dCH₃Qn) < Pt(dCF₃Qn) < Pt(dCF₃Py) < Pt(H₂Qn). The reactivity trends confirm that the quinoline substructure in the (pyrazolylmethyl)quinoline ligands acts as an apparent donor of electron density toward the metal center rather than being a π-acceptor. Measured pK_a values from spectrophotometric acid–base titrations were Pt(H₂Qn) (pK_a1 = 4.56; pK_a2 = 6.32), Pt(dCH₃Qn) (pK_a1 = 4.88; pK_a2 = 6.31), Pt(dCF₃Qn) (pK_a1 = 4.07; pK_a2 = 6.35), and Pt(dCF₃Py) (pK_a1 = 4.76; pK_a2 = 6.27). The activation parameters from the temperature dependence of the second-order rate constants support an associative mechanism of substitution.     

Ruthenium Carbonyl Cluster Complexes with Phenylgermyl Ligands from the Reactions of Ph<Subscript>3</Subscript>GeH with Ru(CO)<Subscript>5</Subscript> and Ru<Subscript>3</Subscript>(CO)<Subscript>12</Subscript>

Four new triphenylgermylruthenium carbonyl compounds HRu(CO)₄GePh₃, 14; Ru(CO)₄(GePh₃)₂, 15; Ru₂(CO)₈(GePh₃)₂, 16; and Ru₃(CO)₉(GePh₃)₃(μ-H)₃, 17 were obtained from the reaction of Ru(CO)₅ with Ph₃GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)₅ and an oxidative addition of the GeH bond of the Ph₃GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh₃ ligands in the six coordinate complex. Compound 16 contains two Ru(CO)₄(GePh₃) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh₃ ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru₃(CO)₁₀(μ-GePh₂)₂, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh₂ ligands bridging two different edges of the cluster and one bridging CO ligand. Ru₃(CO)₁₂ was found to react with Ph₃GeH at 97 °C to yield three products: 15, and two new compounds Ru₃(CO)₉(μ-GePh₂)₃, 19 and Ru₂(CO)₆(μ-GePh₂)₂(GePh₃)₂, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh₂ ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh₂ ligands and a terminal GePh₃ ligand on each metal atom. All compounds were characterized by a combination of IR, ¹H NMR, single-crystal X-ray diffraction analyses. This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions to the chemistry of metal chalcogenide cluster complexes.