Synthesis and reactions of a nucleophilic bis(μ-dimethylphosphido)dicobalt complex. The crystal and molecular structure of [C5H5Co(μ-PMe2)]2 and [(C5H5Co)2(μ-H)(μ-PMe2)2]BPh4

Site Selectivity in the Protonation of a Phosphinito Bridged PtI−PtI Complex: a Combined NMR and Density-Functional Theory Mechanistic Study

“…Although deprotonation of bridging hydrido complexes has been reported for Co 2 , 45 Rh 2 , 46 Mo 2 , 47 Mo-Mn, 48 Os 3 , 49 Mo-Pt or W-Pt 50 systems, to the best of our knowledge no example is known to date of a reversible protonation of a Pt-Pt bond. 51 Such a behavior may be favored in the present case by the possibility of the phosphinite to rebind the Pt 1 restoring the κ 2 -P,O bridge.…”

“…On the contrary, a variety of protonation products can be obtained when the two metals are bridged by a phosphanido group. Bridging hydrides are formed by protonation of [Fe 2 (μ-A)(μ-A′)(CO) 4 L 2 ] [A = A′= PPh 2 , PMe 2 ; A = SPh, A′ = PPh 2 ; L = P(CH 3 ) 3− x (C 6 H 5 ) x ], [NEt 4 ][(CO) 4 Mn(μ-PTol 2 )Mo(CO) 2 Cp] ( Mn−Mo ), [Cp 2 Co 2 (μ-PR 2 ) 2 ] (PR 2 = PMe 2 , PPh 2 , PEt 2 , PMePh, 1 / 2 Ph 2 P(CH 2 ) n PPh 2 , n = 2 or 3), [CpMo(μ-PPh 2 )CO)] 2 , [m(μ-PPh 2 )Pt(PPh 3 ) 2 ] [m = W(CO) 2 Cp, Mn(CO) 4 , Co(CO) 3 ], [Cp*Rh(μ-PMe 2 )] 2 , or [Cp(CO) 2 Mo(μ-PPh 2 )Pt(CO)(PPh 3 )] . Interestingly, the related complexes [Cp(CO) 2 W(μ-PPh 2 )Pt(CO)(PPh 3 )] and [Cp(CO) 2 W(μ-PCy 2 )Pt(CO)(PCy 2 H)] give, the first protonation directly at the tungsten to give [Cp(CO) 2 (H)W(μ-PPh 2 )Pt(CO)(PPh 3 )] + , the second both isomeric hydrides [Cp(CO) 2 W(μ-PCy 2 )(μ-H)Pt(CO)(PCy 2 H)] + and [Cp(H)(CO) 2 W(μ-PCy 2 )Pt(CO) (PCy 2 H)] + of which the former is the major product …”

Metallkomplexe mit verbrückenden Dimethylphosphido‐Liganden, V Additions‐ und Insertionsreaktionen des Zweikernkomplexes [C5H5Co(μ‐PMe2)]2 mit Alkinen

“…B. CF3C02H) unter Angriff des Protons an der Co -Co-Bindung und Bildung des Kations [(CSHSCo)2(p-PMe,),(p-H)] + 8, 9). Unter gleichen Bedingungen findet auch eine Protonierung des Komplexes 6 statt.…”

Synthesis of a carborane-substituted bis(phosphanido) cobaltate(i), ligand substitution, and unusual P4fragmentation

“…X-ray crystallographic analysis (vide infra) revealed the structure of the complex dianion [rac-9] 2 ⁻, which features a bridging, open-chain In all complexes, the C−C bond within the ortho-carborane backbone is in the typical range for carborane-substituted bis(phosphane) complexes. 27,50 In the case of the complex anions [rac-1] − , [rac-6] − and [rac-9] 2− , the Co−P bonds formed by the bis(phosphanido) ligand are in the range of single bonds, [51][52][53][54][55][56][57][58][59] and significantly elongated compared to IV (2.1437(5) Å), consistent with the lower oxidation state of the metal (vide infra). For these complexes, the sums of bond angles around the phosphorus atoms range from 328.5(2)°([rac-6] − ) to 340.7( 7)° ([rac-9] 2− ), showing significant pyramidalisation.…”