Manganese Containing Heterometallic Clusters Containing Ligands Derived from Elements of Groups 15 and 16

The area of manganese-containing mixed-metal clusters is reviewed. Discussion is divided into two sections: that containing clusters bridged by ligands derived from elements of Group 15 and those containing ligands derived from the Group 16 elements of the Periodic Table. Emphasis is given to synthetic strategies and those reactivity features which result in Mn-containing new cluster formations. Dedicated to Professor Dr. Dieter Fenske on the occasion of his 65th birthday. Yuri V. Torubaev is on leave from the N.S. Kurnakov Institute of General and Inorganic Chemistry, Leninskii Prospeckt, Moscow, Russia     

Synthesis,Structure, and Haptotropic Interconversions of Tungsten Cycloheptatrienyl–Acetonitrile–Carbonyl Complexes

Russian Journal of Coordination Chemistry - Tungsten cycloheptatrienyl complexes (η7-C7H7)W(CO)2I (I), [(η3-C7H7)W(CO)2(CH3CN)3]PF6 (II), and [(η7-C7H7)W(CO)2(CH3CN)]PF6 (III) (CIF...     

The Shortened Transition Metal–Tellurium Bonds in Organometallic Clusters

The shortening of partly multiple M–Te (M = Mn, Fe, Co, Cr or W) bonds is observed for two classes of organometallic compounds: (1) formally electron-deficient species with additional donor–acceptor interaction between Te lone pairs and half-occupied d-orbitals of M; (2) formally electron-saturated species having additional dative interaction between M lone pairs and LUMO of Te. These compounds could be prepared by two main methods: (a) interaction of [CpMn(CO)₂PhC(O)⁻]Li⁺ with Te proceeds via formation of intermediate {[CpMn(CO)₂]₂Te}²⁻ which is further transformed into binuclear complex [CpMn(CO)₂]₂Te(CH₂Ph)₂ or into trinuclear ditelluride cluster [CpMn(CO)₂]₃Te₂ on one hand or to mixed-metal monotelluride clusters [CpMn(CO)₂]₂TeM(CO)₅ on another hand. (b) treatment of Fe(CO)₅, CpMn(CO)₂(THF) or Me₄C₄Co(CO)₂I with [PhTeI]₄, PhTeI₃ or PhTeI₂HC = CPhI results in different PhTeI-containing complexes of Fe, Mn or Co. The molecular structures of all new compounds were studied by means of X-ray diffraction analyses and the mechanism of M–Te bond shortening is discussed. Proceeding of the international workshop on transition metal clusters, 3–5 July 2008, Université de Rennes 1, Campus de Beaulieu, Rennes, France.     

Synthesis and molecular structures of cyclopentadienyl sulfide complexes of chromium with cymantrenyl-thiolate bridging ligands

Interaction of [Cp₂Cr₂(CO)₄[μ-SC₅H₄Mn(CO)₃]₂ with sulphur gave binuclear complex Cp₂Cr₂[μ-SC₅H₄Mn(CO)₃]₂(μ-S) (I) (Cp = π-C₅H₅) and triangular cluster Cp₃Cr₃[μ-SC₅H₄Mn(CO)₃](μ-S)₂(μ₃-S) (II). I was also synthesized from Cp₂Cr₂(μ-SCMe₃)₂(μ-S) and (CO)₃Mn(C₅H₄SH). Interaction between I and Co₂(CO)₈ resulted in triangular mixed-metal cluster Cp₂Cr₂[μ-SC₅H₄Mn(CO)₃](μ³-S)₂Co(CO)₂ (III). The molecular structures of I–III were determined by means of single-crystal X-ray diffraction analysis.     

Unusual Formation of the Paramagnetic Complex (η4-C4Me4)CoI2(PhTeI) and Specific Features of Its Electronic,Molecular, and Crystal Structures

Russian Journal of Coordination Chemistry - The 18-electron (η4-C4Me4)Co(CO)2TeI2Ph compound noticeably decomposes upon prolonged storage and also unusually transforms into the 17-electron...     

Synthesis and molecular structures of the cobalt complexes (η4-C4Me4)Co(CO)2SnCl3, (η4-C4Me4)Co(CO)2(TeI2Ph), and (η4-C4Me4)Co(CO)2 (TeBrIPh) with the shortened Co-Sn and Co-Te bonds

The complex (η⁴-C₄Me₄)Co(CO)₂I (I) reacted with excess SnCl₂ in boiling THF to give, through replacement of the iodide ligand by the fragment SnCl₃, the mononuclear complex (η⁴-C₄Me₄)Co(CO)₂SnCl₃ (II) containing the Co-Sn bond (2.459(1) ?). In a reaction of complex I with phenyltellurenyl halides PhTeI and PhTeBr, an analogous insertion into the cobalt-iodine bond yielded (η⁻C₄Me₄)Co(CO)₂(TeI₂Ph) (III) and (η⁴-C₄Me₄)Co(CO)₂(TeBrIPh) (IV), respectively. This type of coordination of the aryltellurenyl halide fragment to the transition metal atom was observed for the first time. X-ray diffraction analysis revealed a substantial shortening of the formally single Co-Sn and Co-Te bonds in complexes II–IV compared to the sum of the covalent radii of the corresponding atoms. Original Russian Text ? Yu.V. Torubaev, A.A. Pasynskii, A.R. Galustyan, p. Mathur, 2009, published in Koordinatsionnaya Khimiya, 2009, vol. 35, No. 1, pp. 3–7.     

Unexpected stabilization of the heterocyclic form of oxidized dithizone: Synthesis and molecular structures of chromium and tungsten 5-mercapto-2,3-diphenyltetrazolium pentacarbonyls

New chromium and tungsten pentacarbonyl complexes with 5-mercapto-2,3-diphenyltetrazole coordinated through the sulfur atom (Cr-S, 2.4655(7) Å; W-S, 2.5755(13) Å) were synthesized and structurally characterized.     

Phenyltellurenyl halide complexes of ruthenium and rhenium (CO)2RuBr2(PhTeBr)2 and (CO)3Re(PhTeI)3(μ3-I): Synthesis and crystal and molecular structures

Reactions of Ru₃(CO)₁₂ with PhTeBr₃ and of Re(CO)₅Cl with PhTeI in benzene give the stable complexes (CO)₂RuBr₂(PhTeBr)₂ (I) and (CO)₃Re(PhTeI)₃(μ³-I) (II) containing two and three ligands PhTeX (X = Br or I), respectively. The bonds between these ligands and the central metal atom are fairly shortened (on average, Ru-Te, 2.608 ?; Re-Te, 2.7554(12)-2.7634(13) ?). The Te-X bonds in the ligands PhTeBr (2.5163(5) ?) and PhTeI (2.7893(15) ?) are not lengthened appreciably. In complex II, the iodide anion is not coordinated by rhenium, yet being attached through weak secondary bonds to three Te atoms of the three ligands PhTeI.     

Stannylene complexes of manganese,iron, and platinum

A number of stannylene complexes with different M: Sn ratios were obtained using various metals and substituents at the tin atom. The structures of the complexes were examined. A reaction of CpMn(CO)₂THF with (Ph₄As)⁺(SnCl₃)^? gave the ionic complex [Ph₄As]⁺[CpMn(CO)₂SnCl₃]^? (I). The action of C₆F₅MgBr on the complex C₅H₅Mn(CO)(NO)SnCl₃ produced C₅H₅Mn(CO)(NO)Sn(C₆F₅)₃ (II). Replacement of the Cl ions in the complex [CpFe(CO)₂]₂SnCl₂ by phenylacetylenide groups gave rise to the neutral complex [CpFe(CO)₂]₂Sn(C≡CPh)₂ (III). A reaction of (Dppm)PtCl₂ (Dppm is 1,1-bis(diphenylphosphino)methane) with SnCl₂ · 2H₂O in the presence of diglyme yielded the ionic complex [η³-CH₃O(CH₂)₂O(CH₂)₂OCH₃)SnCl]⁺[(η ²-Dppm)Pt(SnCl₃)₃]^? (IV). Transmetalation in a reaction of [(Dppe)₂CoCl][SnCl₃] · PhBr (Dppe is 1,2-bis(diphenylphosphino)ethane) with (Dcpd)PtCl₂ (Dcpd is dicyclopentadiene) in the presence of SnCl₂ afforded the ionic complex [Pt(Dppe)₂]₃[Pt(SnCl₃)₅]₂ (V). Structures I–V were identified by X-ray diffraction. In these structures, the formally single bonds between the atoms of transition metals M (Mn, Fe, and Pt) and Main Group heavy elements (Sn and P) having vacant d orbitals are appreciably shortened. The M-Sn bond length in complexes II and III are virtually independent of the substituents at the tin atom and the Pt-Sn bond length in complexes IV and V is virtually independent of the Pt: Sn ratio.