Impact of the Methylene Bridge Substitution in Chelating NHC-Phosphine Mn(I) Catalyst for Ketone Hydrogenation.

Systematic modification of the chelating NHC-phosphine ligand (NHC = N-heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac-[(PhPCHNHC)Mn(CO)Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000-20000.

Phosphine-NHC-Phosphonium Ylide Pincer Ligand: Complexation with Pd(II) and Unconventional -Coordination of the Ylide Moiety.

An efficient synthesis of two pincer preligands [PhPCH(R)ImCHCHCHPPh]X (R = H, X = OTf; R = Ph, X = BF) was developed. Subsequent reactions with PdCl and an excess of CsCO led to the formation of highly stable cationic metalated Pd(II) complexes [(,,,)Pd]X exhibiting phosphine, NHC, phosphonium ylide, and σ-aryl donor extremities. The protonation of one of the latter complexes with R = H affords the Pd(II) complex [(,,)Pd(MeCN)](OTf) bearing an unprecedented nonsymmetrical NHC core pincer scaffold with a 5,6-chelating framework.

Phosphine-NHC Manganese Hydrogenation Catalyst Exhibiting a Non-Classical Metal-Ligand Cooperative H Activation Mode.

Deprotonation of the Mn NHC-phosphine complex fac-[MnBr(CO) (κ P,C-Ph PCH NHC)] (2) under a H atmosphere readily gives the hydride fac-[MnH(CO) (κ P,C-Ph PCH NHC)] (3) via the intermediacy of the highly reactive 18-e NHC-phosphinomethanide complex fac-[Mn(CO) (κ P,C,C-Ph PCHNHC)] (6 a). DFT calculations revealed that the preferred reaction mechanism involves the unsaturated 16-e mangana-substituted phosphonium ylide complex fac-[Mn(CO) (κ P,C-Ph P=CHNHC)] (6 b) as key intermediate able to activate H via a non-classical mode of metal-ligand cooperation implying a formal λ -P-λ -P phosphorus valence change. Complex 2 is shown to be one of the most efficient pre-catalysts for ketone hydrogenation in the Mn series reported to date (TON up to 6200).

Manganese-mediated synthesis of an NHC core non-symmetric pincer ligand and evaluation of its coordination properties.

The alkylation of N-(2-pyridyl)imidazole by the Mn methylene-phosphonium complex [Cp(CO)Mn(η-P,C-PhP[double bond, length as m-dash]C(H)Ph)]BF offers a straightforward route to a tridentate pro-ligand featuring an NHC core and phosphine/pyridine arms. The ability of this PĈN ligand to coordinate in a pincer mode was recognized in Rh, Rh, and Ni complexes.