[{Cp″Co}3(μ3-P)(μ3-PSe)], ein Dreikerncluster mit einem PSe-Liganden

[{Cp″Co}₃(μ₃-P)(μ₃-PSe)], a Trinuclear Cluster with a PSe Ligand The cothermolysis of [Cp″Co(CO)₂] ( 1 ), Cp″ = C₅H₃Bu-1.3, and P₄ gives besides [{Cp″Co}₃(μ₃-P)₂] ( 2 ) the cobalt P_n complexes [{Cp″Co}₄(μ₃-P)₄] ( 3 ) and [{Cp″Co}₂(μ, η^2:2-P₂)₂] ( 4 ). 2 can be oxidized with grey selenium forming [{Cp″Co}₃(μ₃-P)(μ₃-PSe)] ( 5 ) and [{Cp″Co}₃(μ₃-PSe)₂] ( 6 ), complexes with the hitherto unknown PSe ligand. The crystal structure of 5 reveals a trigonal-bipyramidal Co₃P₂ skeleton with one μ₃-PSe ligand.     

The new polynuclear titanium(IV) complex [(Cp*TiCl)(μ‐O)2(Cp*Ti)2(μ‐O)(μ‐O)2]2Ti (Cp* is η5‐C5Me5)

A new polynuclear titanium(IV) complex, dichloro­deca‐μ₂‐oxo‐hexa­kis­(penta­methyl­cyclo­penta­dien­yl)hexa­titanium(IV), [Ti₆(C₁₀H₁₅)₆Cl₂O₁₀], has been synthesized by hydro­lysis of a titanium complex bearing an N‐(2‐hydr­oxy‐3,5‐dimethyl­benz­yl)diethano­lamine Mannich ligand. The mol­ecule has two O‐bridged Ti₃O₃ rings linked to two similar rings through a tetra­hedrally O‐coordinated Ti atom. All Ti atoms except the central one are coordinated to penta­methyl­cyclo­penta­dien­yl (Cp*) ligands. The Cp* ligands are arranged with approximate symmetry with respect to the Ti/O/Cl core.     

The preparation and crystal structure of trinuclear molybdenum compound (Me4N)[Mo3(μ3-O)(μ-Cl)3(μ-O2CH)3Cl3]

The title compound was prepared by the oxidation of MoCl₃ in liquid phase. The crystal belongs to the orthorhombic system with space group D-Pmnb and unit cell parameters: a = 11.403 (1), b = 12.345 (2), c = 14.292 (2) Å; V = 2011.8 ų; Z = 4, D_c = 2.396g/cm³. Altogether 2303 independent reflections were collected on a CAD-4 four-circle diffractometer with Mo Kα radiation in range 2° ≤ θ ≤ 27°. The crystal structure was solved by heavy-atoms method and refined by full-matrix least-squares technique to final discrepancy factors R = 0.050 and R_w= 0.056 for 1513 reflections of I ≥ 3σ (I). The configuration of the cluster anion was characterized to be of the same Ml type structure as presented in the previous paper. The average bond lengths of Mo—Mo and Mo-(μ₃-O) are 2.577 Å and 1.982 Å respectively. In addition, the effects of bridging atoms, other ligands and bond orders on Mo—Mo bonds are discussed briefly.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.