Phosphinite-Ni(0) Mediated Formation of a Phosphide-Ni(II)-OCOOMe Species via Uncommon Metal–Ligand Cooperation

Abstract

Reversible transformations are observed between a phosphide-nickel(II) alkoxide and a phosphinite-nickel(0) species via a P-O bond formation coupled with a 2-e(-) redox change at the nickel center. In the forward reaction, the nickel(0) dinitrogen species (PP(OMe)P)Ni(N2) (2) and {(PP(OMe)P)Ni}2(μ-N2) (3) were formed from the reaction of (PPP)NiCl (1) with a methoxy anion. In the backward reaction, a (PPP)Ni(II) moiety was regenerated from the CO2 reaction of 3 with the concomitant formation of a methyl carbonate ligand in (PPP)Ni(OCOOMe) (7). Thus, unanticipated metal-ligand cooperation involving a phosphide based ligand is reported.

Addition of H2 Across a Cobalt–Phosphorus Bond

“…Both stoichiometric and catalytic reactions involving the addition of s bonds across metal-element bonds (element = N, O, C, B, S) have become increasingly prevalent. [25][26][27][28][29][30][31][32] In av ery recent paper by Gudat and coworkers,ametal phosphenium complex, (uNHP Dipp )Mn(CO) 4 (where NHP R indicates amonodentate NHP + cation with N-Rs ubstituents," u" indicates an unsaturated backbone,a nd Dipp = 2,6-diisopropylphenyl), was shown to be an active catalyst for the catalytic dehydrogenation of NH 3 BH 3 . [21][22][23][24] Related examples of metalligand cooperativity involving phosphorus are far less common.…”

“…[21][22][23][24] Related examples of metalligand cooperativity involving phosphorus are far less common. [25][26][27][28][29][30][31][32] In av ery recent paper by Gudat and coworkers,ametal phosphenium complex, (uNHP Dipp )Mn(CO) 4 (where NHP R indicates amonodentate NHP + cation with N-Rs ubstituents," u" indicates an unsaturated backbone,a nd Dipp = 2,6-diisopropylphenyl), was shown to be an active catalyst for the catalytic dehydrogenation of NH 3 BH 3 . (uNHP Dipp -H)Mn(H)(CO) 3 could be generated through sequential addition of ah ydride and ap roton to (uNHP Dipp )Mn(CO) 4 ,and H 2 elimination could be promoted by photolysis;however, direct H 2 addition to (uNHP Dipp )Mn-(CO) 4 was not possible.…”

[NiIII(OMe)]-mediated reductive activation of CO2 affording a Ni(κ1-OCO) complex

“… 1 , 2 Nature developed carbon monoxide dehydrogenase (CODH) to harbor a Ni–Fe cluster for the reversible interconversion between CO 2 and CO. 3 – 5 To gain insight into the mechanism for the conversion of CO 2 to CO in CODH, several Ni–CO 2 adducts derived from the reaction of a low-valent Ni complex and CO 2 were reported. 6 – 9 The direct electrochemical reduction of CO 2 affords oxalate, carbon monoxide, formic acid, methanol, methane, and ethylene. 10 To gain insight into the transformation of CO 2 at a molecular level, the chemistry of the activation of CO 2 via nucleophilic attack/interaction on the polarized C center, in addition to the reduction of the coordinated CO 2 ligand by low-valence transition metal complexes, has grown explosively over past years.…”

Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane

“…66, 67 In such transformations, there is an apparent connection to be made to migration reactivity to/from lower coordinate phosphorus ligands (i.e. phosphenium, 68 - 70 phosphide 71, 72 , phosphinidene 73-76 ).…”