Platinum–manganese and –rhenium complexes with bridging thiocarbonyl ligands; crystal structure of [Mnpt(µ-CS)(CO)₂(PMePh₂)₂(η-C₅H₅)]

Abstract

The dynamic complexes [MPt(p-CS) (CO),-(PR3),(q-C5H5)] (M = Mn, PR, = PMe,Ph oi-PMePh,; M = Re, PR, = PMe,Ph) have been prepared by allowing the compounds [M(CO),(CS) (q-C,H,)] to react with the species [Pt(C,H,) (PR,),], and an X-ray diffraction study on [MnPt(p-CS) (C0),(PMePh,),(q-C5H5)] has confirmed the presence of the bridging thiocarbonyl ligand and revealed a strongly semi-bridging CO group.

Unusual reactions of cationic carbyne complexes of manganese and rhenium with [NMe4][HFe(CO)4] to form heteronuclear dimetal carbene-bridged complexes

“…It is equally interesting that complex 7 when treated with PPh 3 in thf at Ϫ55 to 0 ЊC gave [ReFe{µ-C(H)Ph}(η-C 5 H 5 )(CO) 5 (PPh 3 )] 9, in which a CO ligand on iron has been displaced by PPh 3 , in 52% yield. Unexpectedly, the reaction of 5 with PPh 3 under the same conditions gave no analogous PPh 3 -substituted complex, as in the reaction of [PtW{µ-η 1 : 16 or complex 7 with PPh 3 , but decomposition products such as [Fe(CO) 3 (PPh 3 ) 2 ]. 17 Complexes 5, 8 and 9 are readily soluble in polar organic solvents but slightly soluble in non-polar solvents, and sensitive to air and temperature in solution but relatively stable as solids.…”

“…] which showed dynamic behaviour for the tolyl group at 25 ЊC, ceasing at Ϫ70 ЊC. 16 The Mn-Fe distance of 2.770( 7 The molecular structure of complex 8 (Fig. 2) shows that the benzene ring is still bonded to the Fe atom, and a formyl (C᎐ ᎐ O) group is bonded to the original alkylidene carbon [C (11)] and the Fe atom through the C( 18) atom and provides one electron for the Fe atom to satisfy an 18-electron configuration.…”

Syntheses and dynamic stereochemistry of methyl–and phenyl–carbonyl heterobinuclear metal–metal bonded complexes

“…It has not been possible to isolate the trans isomer of ( 1 ) in a pure form owing to its high tendency to decompose. On the other hand, there is no evidence for the formation of trans- (2) after allowing the toluene solutions of the cis isomer to reach room temperature. Decomposition has precluded its characterization and corresponds to a lower stability of the bimetallic tungsten derivatives with respect to their molybdenum analogues.…”

Reactions of co-ordinated ligands. Part 36. The synthesis, structure, and reactivity of the three-alkyne ‘fly-over’ complex [Mo2{µ-(σ,η3:η3,σ-C6Me6)}(η5-C9H7)2]; formation and structure of [Mo2{µ-(σ,η3:η3,σ-C6Me6)}(CO)2(η5-C9H7)2]

“…. This bond [C(3)4(4) 1.493(16) A in (1) and 1.515(7) A in (2)] is the longest within the six-carbon chain in both (1) and (2) [cf. the C-Me distances in the range 1.507-1.543 A in (1) and (2)], as would be expected since the substantial twisting about C(3)-C(4) will reduce the n: interaction between the planar allylidene subunits.…”