Syntheses and molecular structures of Ru3(μ-H)(μ3-CPh2CCCCPh)(CO)9 and Ru3{μ3-CPhCHCC(CPh2)CHCPh}(μ-CO)(CO)8

The reaction between Ru₃(μ-H){μ₃-C₂CPh₂(OH)}(CO)₉ and HCCPh, carried out in the presence of HBF₄ · Me₂O, afforded the cluster complexes Ru₃(μ-H)(μ₃-CPh₂CCCCPh)(CO)₉ (5) and Ru₃{μ₃-CPhCHCC(CPh₂)CHCPh}(μ-CO)(CO)₈ (6), both of which were characterised by single-crystal X-ray studies.     

Two gold-ruthenium clusters derived from Ru3(μ-H)3(μ3-CBr)(CO)9

The reaction between AuMe(PPh₃) and Ru₃(μ-H)₃(μ₃-CBr)(CO)₉ (1) affords the novel heptanuclear cluster Au₄Ru₃(μ₃-CMe)(Br)(CO)₉(PPh₃)₃ (2), containing an Au/Ru₃/Au trigonal pyramidal cluster face-capped by two Au(PPh₃) groups and a CMe ligand, together with Au₂Ru₃(μ-H)(μ₃-CMe)(CO)₉(PPh₃)₂ (3), formed by isolobal replacement of two of the three μ-H atoms in 1 by Au(PPh₃) groups. The latter co-crystallises with the analogous μ₃-CH complex, as also shown spectroscopically.     

Synthesis and molecular structure of [((CO)3RuBr2)2(μ-SePh)2Ru(CO)4] cluster with a Ru3Se2 chain core

Treatment of ruthenium carbonyl, [Ru₃(CO)₁₂] with phenylseleno tribromide PhSeBr₃ afforded a new triruthenium cluster, [(CO)₁₀Br₄Ru₃(μ-SePh)₂] (1). Its molecular structure was determined by single crystal XRD method (P2₁/c; a = 10.514(3) Å; b = 10.814(3) Å; c = 19.063(5) Å; β = 105.064(4)°; V = 2093.1(10) Å³) and shown to have two lateral Ru(CO)₃Br₂ units attached via two PhSe bridges to a Ru(CO)₄ center forming a chain-like Ru-Se-Ru-Se-Ru cluster core. This is in contrast with a recently reported reaction of PhTeBr₃ with [Ru₃(CO)₁₂] which formed a monomeric complex of ruthenium-dicarbonyl-dibromo fragment coordinating two PhTeBr ligands, [(CO)₂RuBr₂(PhTeBr)₂].     

The reaction of Ru3(CO)12 with 1,4-dichloro-but-2-yne in basic methanolic solution. Synthesis and crystal structure of (μ-H)2Ru3(CO)9{μ3-η-[H2CC(H)CCC(O)OCH3]}

The title complex is obtained by reacting Ru₃(CO)₁₂ with 1,4-dichloro-but-2-yne (ClCH₂CCCH₂Cl, DCB) in CH₃OH/KOH solution (followed by acidification with HCl). The X-ray structure analysis shows that (μ-H)₂Ru₃(CO)₉{μ₃-η²-[H₂CC(H)CCC(O)OCH₃]} complex contains a “parallel” ene-yne acetyl substituent, H₂CC(H)CCC(O)OCH₃; the formation of such a ligand starting from DCB is - to our knowledge - unprecedented. The synthesis of complex (μ-H)₂Ru₃(CO)₉{μ₃-η²-[H₂CC(H)CCC(O)OCH₃]} occurs through the activation of CO and methanol. This process has been found for other reactions of functionalized alkynes with M₃(CO)₁₂ carbonyls (M = Fe, Ru) under basic methanolic conditions.The known hydridic cluster, (μ-H)Ru₃(CO)₉[μ₃-η³-(MeCCHCH)] has been identified as the minor reaction product.     

Synthesis, Molecular Structure and Derivatization of the Triruthenacarborane Cluster Compound [1-SMe2-2,2-(CO)2-7,11-(Μ-H)2-2,7,11-{Ru2(CO)6}-closo-2,1-RuCB10H8]*

In toluene at reflux temperatures [Ru₃(CO)₁₂] and 7-SMe₂-nido-7-CB₁₀H₁₂ give the charge-compensated cluster complex [1-SMe₂-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(CO)₆-closo-2,1-RuCB₁₀H₈] (1) . Treatment of 1 with dppm in THF affords [1-SMe₂-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(μ -dppm)(CO)₄-closo-2,1-RuCB₁₀H₈] (2) [dppm = bis(diphenylphosphino)methane; THF = tetrahydrofuran]. The latter complex on heating in THF with [ ]F yields the salt [ ][1-SMe-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(μ -dppm)(CO)₄-closo-2,1-RuCB₁₀H₈] (3). Reaction of 3 with [AuCl(PPh₃)] and Tl[PF₆] gives the neutral zwitterionic complex [1-S(Me)Au (PPh₃)-2,2-(CO)₂-7,11-(μ-H)₂-2,7,11-Ru₂(μ-dppm)(CO)₄-closo-2,1-RuCB₁₀H₈] (4). The structures of 1, 3 and 4 were determined by single-crystal X-ray diffraction studies.*Dedicated to Professor F. Albert Cotton on the occasion of his 75th birthday, in appreciation of our long friendship and in recognition of his outstanding contributions to the study of complexes with metal–metal bonds.     

Synthesis, structure and electrochemistry of CO incorporated diruthenium metallacyclic compounds [Ru2(CO)6{μ-η:η:η:η-1,4-Fc2C5H2O}] and [Ru2(CO)6{μ-η:η:η:η-1,5-Fc2C5H2O}]

Ferrocenyl substituted ruthenium metallacyclic compounds, [Ru₂(CO)₆{μ-η¹:η¹:η²:η²-1,4-Fc₂C₅H₂O}] (1) and [Ru₂(CO)₆{μ-η¹:η¹:η²:η²-1,5-Fc₂C₅H₂O}] (2) have been synthesized and structurally characterized. Electrochemical studies for 1 and 2 and the respective quinone derivatives 3 and 4 show weak to no electrochemical coupling at the mixed-valent intermediate state which is dependent on the complex frameworks.     

Ru2(CO)4{OOC(CH2)nCH3}2L2 sawhorse-type complexes containing μ2-η2-carboxylato ligands derived from saturated fatty acids

The thermal reaction of Ru₃(CO)₁₂ with the saturated fatty acids (heptanoic, nonanoic, decanoic, tridecanoic, tetradecanoic, heptadecanoic, octadecanoic) in refluxing tetrahydrofuran, followed by addition of triphenylphosphine (PPh₃) or pyridine (C₅H₅N), gives the dinuclear complexes Ru₂(CO)₄{OOC(CH₂) _n CH₃}₂L₂ (1: n = 5, 2: n = 7, 3: n = 8, 4: n = 11, 5: n = 12, 6: n = 15, 7: n = 16; a: L = NC₅H₅, b: L = PPh₃). The single crystal structure analysis of 1b, 2a, 3a, 4a and 5a reveals a dinuclear Ru₂(CO)₄ sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two L ligands occupy the axial positions at the ruthenium atoms. In 2a, π-π stacking interactions between adjacent pyridyl units of symmetry related molecules prevail, while in the longer alkyl chain derivatives 3a, 4a and 5a, additional van der Waals and electrostatic interactions between the alkyl chains take place as well in the packing arrangement of the molecules, thus giving rise to layers of parallel alkyl chains in the crystal.     

Synthesis of electronically and coordinatively unsaturated complexes [Ru2(CO)4(μ-H)(μ-PBu2)(μ-L2)] (L2 = biphosphanes)

A convenient synthesis and the characterization of six new electronically and coordinatively unsaturated complexes of the formula [Ru₂(CO)₄(μ-H)(μ-P^tBu₂)(μ-L₂)] (2b-g) (RuRu) is described exhibiting a close relation to the known [Ru₂(CO)₄(μ-H)(μ-P^tBu₂)(μ-dppm)] (2a). The complexes 2b-g were obtained in a kind of one-pot synthesis starting from [Ru₃(CO)₁₂] and P^tBu₂H in the first step followed by the reaction with the bidentate bridging ligand in the second step. The method was developed for the following bridging ligands (μ-L₂): dmpm (2b, dmpm = Me₂PCH₂PMe₂), dcypm (2c, dcypm = Cy₂PCH₂PCy₂), dppen (2d, dppen = Ph₂PC(=CH₂)PPh₂), dpppha (2e, dpppha = Ph₂PN(Ph)PPh₂), dpppra (2f, dpppra = Ph₂PN(Pr)PPh₂), and dppbza (2g, dppbza = Ph₂PN(CH₂Ph)PPh₂). The molecular structures of all new complexes 2b−g were determined by X-ray diffraction.     

Nitrosyl derivatives of the unsaturated dihydrides [Mn2(μ-H)2(CO)6(μ-L2)] (L2 = Ph2PCH2PPh2, (EtO)2POP(OEt)2)

The title dimanganese complexes react with NO (5% in N₂) at room temperature to give as major products the corresponding hexanitrosyl derivatives [Mn₂(NO)₆(μ-L₂)] in moderate yields, and they react rapidly with NO₂ to give the corresponding hydride derivatives [Mn₂(μ-H)(μ-NO₂)(CO)₆(μ-L₂)], these having a nitrite ligand bridging the dimetal centre through the N and O atoms. The dppm-bridged dihydride also reacts selectively at 273 K with (PPN)NO₂ to give first the nitro derivative (PPN)[Mn₂(μ-H)(H)(NO₂)(CO)₆(μ-dppm)], which then transforms into the nitrosyl complex (PPN)[Mn₂(μ-CO)(CO)₅(NO)(μ-dppm)] at room temperature or above (dppm = Ph₂PCH₂PPh₂; PPN⁺ = [N(PPh₃)₂]⁺). The latter anion reacts with (NH₄)PF₆ to give the hydride-bridged nitrosyl complex [Mn₂(μ-H)(μ-NO)(CO)₆(μ-dppm)] and with [AuCl(PPh₃)] to give the trinuclear cluster [AuMn₂(μ-NO)(CO)₆(μ-dppm)(PPh₃)] (Mn-Au = ca. 2.68 Å; Mn-Mn = 2.879(2) Å). Both products are derived from the addition of the added electrophile at the intermetallic bond and rearrangement of the nitrosyl ligand into a bridging position. In contrast, methylation of the anion with CF₃SO₃Me takes place at the nitrosyl ligand to yield the unstable methoxylimide derivative [Mn₂(μ-NOMe)(CO)₆(μ-dppm)]. Analogous reactions at the nitrosyl ligand take place upon the addition of HBF₄·OEt₂ to the nitrosyl-bridged hydrides [Mn₂(μ-H)(μ-NO)(CO)_n(μ-dppm)_m] (n = 6, m = 1; n = 4, m = 2) to give the corresponding hydroxylimide derivatives [Mn₂(μ-H)(μ-NOH)(CO)_n(μ-dppm)_m]BF₄, which were also thermally unstable and could not be isolated nor fully characterized.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

The structurally characterised silyl complexes, Os(κ-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 and Os(κ-S2CNMe2)(SiCl3)(CO)(PPh3)2, which have remarkably unreactive Si-Cl bonds

Treatment of Os(κ²-S₂CNMe₂)H(CO)(PPh₃)₂ with HSiMeCl₂ or HSiCl₃ gives in high yield Os(κ²-S₂CNMe₂)(SiMeCl₂)(CO)(PPh₃)₂ (1) or Os(κ²-S₂CNMe₂)(SiCl₃)(CO)(PPh₃)₂ (2), respectively. The crystal structures of both compounds have been determined and the Os-Si distances are 2.3672(10) Å for 1 and 2.3449(12) Å for 2. In solution, and under forcing conditions, both compounds are extraordinarily unreactive towards hydroxide ions.     

对苯二甲酸二丙炔醇酯与Co2(CO)8、Mo2Cp2(CO)4和RuCo2(CO)11的反应

室温下对苯二甲酸二丙炔醇酯分别与Co2CO8Mo2Cp2CO4和RuCo2CO11反应得到三个有机金属化合物C6H4pCO2CH2C2Hμ2Co2CO621、C6H4pCO2CH2C2H2RuCo2CO922和HC2CH2OCOC6H4pCO2CH2C2HμMo2Cp2CO43。研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2CO9>Co2CO6>Mo2CO4Cp2。化合物1的晶体衍射发现属三斜晶系空间群a=8.1392b=8.8083c=11.3433β=96.2606°V=773.443Z=1Dc=1.748g·cm-3R=0.0513wR=0.1266。     

Soft activation of the C-S bond: X-ray diffraction and spectroscopic study of the cluster Ru4(μ4-S)(μ,η3-C3H5)2(CO)12

The complex Ru₄(μ₄-S)(μ,η³-C₃H₅)₂(CO)₁₂ is prepared and examined by IR and NMR spectroscopy; its crystal structure is determined (an automatic Bruker-Nonius X8 Apex four-circle diffractometer equipped with a 2-D CCD-detector, 100 K, graphite-monochromated molybdenum source, λ = 0.71073 ?). The crystal belongs to the orthorhombic crystal system with unit cell parameters a = 19.3781(9) ?, b = 12.2898(7) ?, c = 10.1726(4) ?, V = 2422.6(2) ?³, space group Pnma, Z = 4, composition C₁₈H₁₀O₁₂Ru₄S, d _x = 2.343 g/cm³. The molecule of point symmetry C ₁ is situated on the mirror plane of the space group Pnma, two carbonyl groups at Ru2 and Ru3 atoms overlapping with the allylic ligand with a weight of 50% so that carbon atoms coincide. Thus, we have a racemic structure with two overlapping enantiomers of the molecule of Ru₄(μ₄-S)(μ,η³-C₃H₅)₂(CO)₁₂. Original Russian Text Copyright ? 2008 by I. Yu. Prikhod’ko, V. P. Kirin, V. A. Maksakov, A. V. Virovets, and A. V. Golovin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 748–752, May–June, 2008.     

Synthesis and structures of Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O and (NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2] · 6H2O

Single crystals of Cs₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 4H₂O (I) and (NH₄)₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 6H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of both compounds are orthorhombic with the space group Pbam, Z = 2, and unit cell parameters a = 12.0177(3) ?, b = 18.6182(5) ?, c = 6.7573(10) ?, R = 0.0376 (I); a = 11.6539(9) ?, b = 18.3791(13) ?, c = 6.7216(5) ?, R = 0.0179 (II). The main structural units of crystals I and II are [(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂]⁴⁻ chains belonging to the crystal-chemical group A₂K⁰²B₂²M₂¹ (A = UO₂²⁺, K⁰² = C₂O₄²⁻, B² = SO₄²⁻, M¹ = NCS⁻) of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework due to a system of electrostatic interactions with the cesium or ammonium ions in the structure of I. In the structure of II, this framework is additionally stabilized by hydrogen bonds involving the outer-sphere water molecules and ammonium ions. Original Russian Text ? I.V. Medrish, A.V. Virovets, E.V. Peresypkina, L.B. Serezhkina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 7, pp. 1115–1120.     

Thiolate-bridged heterometallic complexes of manganese and platinum: Synthesis and molecular structures of (CO)4Mn(μ-SPh)Pt(PPh3)2, (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO), and (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm)

A reaction of the dimer [Mn(CO)₄(SPh)]₂ with (PPh₃)₂Pt(C₂Ph₂) gave the heterometallic complex (CO)₄Mn(μ-SPh)Pt(PPh₃)₂ (I) and its isomer (CO)₃(PPh₃)Mn(μ-SPh)Pt(PPh₃)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)₃Mn(μ-SPh)Pt(PPh₃)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) ?) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5) and 2.2900(6) ?, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) ?) and the thiolate bridge (Pt-S, 2.332(2) ?; Mn-S, 2.291(2) ?) are retained. In complex III, the Mn-Pt bond (2.623(1) ?) is supplemented with thiolate (Pt-S, 2.341(2) ?; Mn-S, 2.292(2) 0?) and Dppm bridges (Pt-P, 2.240(1)?; Mn-P, 2.245(2) ?). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins.     

Unsaturation in binuclear cyclopentadienylchromium carbonyl thiocarbonyls: Viability of (η-C5H5)2Cr2(CS)2(CO)3 in contrast to (η-C5H5)2Cr2(CO)5

The cyclopentadienylchromium carbonyl thiocarbonyls Cp₂Cr₂(CS)₂(CO)_n (n = 4, 3, 2, 1) have been studied by density functional theory using the B3LYP and BP86 functionals. The lowest energy Cp₂Cr₂(CS)₂(CO)₄ structure can be derived from the experimentally characterized unbridged Cp₂Cr₂(CO)₆ structure by replacing the two terminal carbonyl groups furthest from the Cr-Cr bond with two terminal CS groups. The two lowest energy Cp₂Cr₂(CS)₂(CO)₃ structures have a single four-electron donor η²-μ-CS group and a formal Cr-Cr single bond of length ∼3.1 Å. In contrast to the carbonyl analogue Cp₂Cr₂(CO)₅ these Cp₂Cr₂(CS)₂(CO)₃ structures are viable with respect to disproportionation into Cp₂Cr₂(CS)₂(CO)₄ and Cp₂Cr₂(CS)₂(CO)₂ and thus are promising synthetic targets. The lowest energy Cp₂Cr₂(CS)₂(CO)₂ structures have all two-electron donor CO and CS groups and short CrCr distances around ∼2.3 Å suggesting the formal triple bonds required to give the chromium atoms the favored 18-electron configurations. These Cp₂Cr₂(CS)₂(CO)₂ structures are closely related to the known structure for Cp₂Cr₂(CO)₄. In addition, several doubly bridged structures with four-electron donor η²-μ-CS bridges are found for Cp₂Cr₂(CS)₂(CO)₂ at higher energies. The global minimum Cp₂Cr₂(CS)₂(CO) structure is a triply bridged triplet with a CrCr triple bond (2.299 Å by BP86). A higher energy singlet Cp₂Cr₂(CS)₂(CO) structure has a shorter Cr-Cr distance of 2.197 Å (BP86) suggesting the formal quadruple bond required to give each chromium atom the favored 18-electron configuration.     

A new coordination mode for (pyrid-2-yl)thiolate (L) ligands: Synthesis and characterization of [Ru6(μ3-H)(μ5-κ-L)(μ-CO)(CO)15]

The hexaruthenium cluster complexes [Ru₆(μ₃-H)(μ₅-κ²-L)(μ- CO)(CO)₁₅], HL = 2-mercaptopyridine (1) and 2-mercapto-6-methylpyridine (2), have been prepared by heating [Ru₃(CO)₁₂] with 0.5 equiv. of HL in THF at reflux temperature. An X-ray diffraction study on a crystal of complex 2 has determined that its metallic skeleton, a basal-edge-bridged square pyramid, is hold up by a (6-methylpyrid-2-yl)thiolate ligand. This ligand is attached to the four basal ruthenium atoms of the pyramid through the sulfur atom and to the edge-bridging ruthenium atom through the nitrogen atom. Such a coordination mode is unprecedented for (pyrid-2-yl)thiolate ligands.     

Stable radical adducts of diisopropylphosphoryl radicals with fullerene complexes (η2-C60)Os(CO)(PPh3)2(CNBut) and (η2-C70)Os(CO)(PPh3)2(CNBut)

It was determined by ESR spectroscopy that the UV irradiation of toluene solutions containing Hg[P(O)(OPrⁱ)₂ and the complex (²-C₆₀)Os(CO)(PPh₃)₂(CNBu^t) produces six stable regioisomeric adducts of phosphoryl radicals with complexes, which are not demetallated under UV irradiation and do not dimerize in the absence of UV irradiation. This is caused by the addition of the phosphoryl radicals to the carbon atoms of fullerene localized near the metal-containing moiety. The addition of the phosphoryl radicals to (²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) gives rise to the formation of nine stable regioisomeric radical adducts. A comparison of the composition of regioisomers of the radical adducts of C₇₀ with the phosphoryl radicals, which were formed directly from C₇₀ and from the radical adducts of ²-C₇₀)Os(CO)(PPh₃)₂(CNBu^t) by the demetallation of the latter, revealed an orienting effect of the osmium-containing moiety on the addition of the phosphoryl radicals to the fullerene complex.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1968–1972, September, 2004.     

An anionic binuclear complex of tungsten(II), [(μ-Cl)3{W(SnCl3)(CO)3}2], and its reactivity towards norbornene

An anionic binuclear complex of tungsten(II), [(μ-Cl)₃{W(SnCl₃)(CO)₃}₂]⁻ (1⁻), containing the protonated piperidine molecule [Hpip]⁺ as the counter ion, has been obtained during crystallization of the product from reaction between [W(CO)₄(pip)₂] and SnCl₄ in dichloromethane solution, and its molecular structure has been elucidated by single-crystal X-ray diffraction studies. The chemical properties of complex 1 were investigated by IR and NMR spectroscopy in solution and its catalytic activity was checked in reaction with norbornene (NBE). In the presence of complex 1, NBE transformed to a new olefin, 2,2′-binorbornylidene with ca. 50% yield in dichloromethane solution. The spectroscopic characteristics of complex 1⁻ were compared with those of the reinvestigated analogue compound [(μ-Cl)₃W₂(SnCl₃)(CO)₇] (2). The ¹¹⁹Sn and ¹³C NMR data indicated that in dichloromethane solution complex 2 transformed to the ionic complex 1⁻.