Reactions of [Mo2(μ-RC2R)(CO)4Cp2] (R = CO2Me, Cp = η-C5H5) with P2Ph4, PPh2H and R1SH (R1 = Et, Pri, C6H4Me-p or But): stabilisation of μ-vinyl complexes by chelating substituents

Dithiolene transfer from nickel to a dimolybdenum centre: the first dithiolene alkyne complex

“…General procedures were as described in a previous publication [20]; a Bruker Smart CCD area detector with Oxford Cryosystems low temperature system was used for data collection. Complex scattering factors were taken from the program package SHELXTL SHELXTL [21] as implemented on the Viglen Pentium computer.…”

Divergent Reactivity of a Phosphinidene-Bridged Dimolybdenum Complex Toward 1-Alkynes: P–C, P–H, C–C, and C–H Couplings

“…0.04 Å longer than the corresponding lengths in the mentioned carboxylate-substituted alkenyl complexes, likely reflecting the bulkier nature of the phosphanyl ligand (compared to PCy 2 ) in compounds 3. We note that the trans-dicarbonyl geometry exhibited by these complexes has been structurally characterized also for the carboxylatesubstituted alkenyl complexes 19 and [Mo 2 Cp 2 {- 2 C,O : 2 C,C -CRCHR)(-X)(CO) 2 ] (X= PPh 2 , S i Pr; R = CO 2 Me), 20 and for 21 The geometrical parameters within the phosphanyl ligand of compounds cis-3 and trans-3 are comparable to those observed for the hydride complex 4, 8,9 and deserve no comment. However, the interatomic lengths involving the bridging hydrocarbon group show some differences when compared to those measured in the alkenyl complexes mentioned above.…”

“…28 The ordering of elemental steps from here on is uncertain, and attempting to advance a detailed sequence would be highly speculative. Yet we can assume that, under photochemical conditions, decarbonylation might easily follow alkyne coordination, to give the alkyne-bridged intermediate I3 ( 20,21 Therefore, we can reasonably assume that an intermediate such as I3 (or a closely related one) would analogously rearrange readily into the final complexes of type 3. The elemental steps needed for it are well-precedented in organometallic systems (PH bond cleavage, carbonyl insertion into a MH bond, and formyl/alkyne CC coupling), but the exact sequence of elemental steps is uncertain at the moment.…”

Rh-catalyzed P–P bond activation

“…The presence of the g 2 -P 2 Ph 4 to a single metal center in 2 appears to be unique in that literature precedent demonstrates the propensity of P 2 Ph 4 to bind in a monodentate fashion, or to bridge two metal centers. [19][20][21][22][23][24][25][26][27][28][29] In addition, the related complex Ni(NacNac)(Ph 2 PH) 17 binds only one phosphine ligand yielding the three coordinate species, presumably a result of the slightly larger atomic radius of Rh as well as the aforementioned geometry distortions which accommodate the g 2 -P 2 Ph 4 .…”