Preparation and reactivity of a Ru(0) phosphino–carbene complex

Abstract

The reaction of the phosphino-carbene MeNC3H2NPtBu2 with RuHCl(CO)(PPh3)3 is shown to give facile access to the Ru(0) species (MeNC3H2NPtBu2)Ru(CO)(PPh3)2 (). This species undergoes oxidative addition of H2 and silanes to give (MeNC3H2NPtBu2)RuH2(CO)(PPh3)2, (MeNC3H2NPtBu2)Ru H(SiRPh2)(CO)(PPh3) (R = Ph 5, H 6) and (MeNC3H2NPtBu2) RuH(PhSi(SCH2CH2)2O)(CO)(PPh3) .

Unexpected Vulnerability of DPEphos to C−O Activation in the Presence of Nucleophilic Metal Hydrides

“…[16] However,t his process has only rarely been observed alongside the activation of another ligand, [17] and, certainly not as aroute to the formation of ap hosphinocarbene. [18] The CÀOa ctivation of DPEphos was not restricted to NHCcontaining ruthenium hydride precursors. The reactiono f [Ru(PPh 3 ) 4 H 2 ]w ithD PEphos gave the isolable cis-dihydride complex [Ru(DPEphos) 2 H 2 ]( 5;S upporting Information), [19] which upon heating to 80 8Co vernightu nderwent CÀOa ctivation of one of the DPEphos ligandst oa fford [Ru(DPEphos)-(Ph 2 PC 6 H 4 O)H] (6,S cheme 4).…”

Is the R3Si Moiety in Metal–Silyl Complexes a Z ligand? An Answer from the Interaction Energy

“…The SiEt 3 moiety in CIWJAT10 is most certainly an X‐type ligand, and a formal +V oxidation state can be assigned to the iridium centre. SOKROB appears herein to demonstrate the lower limit of silylicity and has a Π value of 0.59, which is similar to the value determined for FACGIC as both bear two or three strong electron‐donating L‐type ligands (i.e., N ‐heterocyclic carbenes and phosphines) that may contribute to enrichment of the metal centre and consolidation of the bond with the silicon centre. QUINZEU, which was described as a model of the key catalytic intermediate of the iron(0)‐promoted reduction of esters into aldehydes under UV‐light irradiation, reportedly displays no catalytic activity at all.…”