Mechanism of Phosphinidene Complex Arylation by Arylboronic Acids

Abstract

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iPr2N–P═Fe(CO)4 in Olefinic Solvents: A Reservoir of a Transient Phosphinidene Complex Capable of Substrate Hopping

“…Lastly, “bottled” i Pr 2 N–PFe­(CO) 4 was reacted with Grignard reagents to demonstrate a novel approach to form P–C bonds. , Treating 2 (0.1 M in 1-hexene) with phenylmagnesium or vinylmagnesium bromide (1.0 M in THF) at room temperature yielded selectively Fe­(CO) 4 -complexed aminophosphides 10a , b ( 10a : 1.5 h, δ 31 P = 78.7 ppm; 10b : 0.5 h, δ 31 P = 63.5 ppm; Scheme ); these reactions represent unique conversions of P I fragments into P III anions . Subsequent quenching with methanol afforded the secondary aminophosphanes 11 as orange oils in 87–90% yield (δ 31 P = 73.7 ( 11a ), 67.3 ( 11b ) ppm; Scheme ), which are the formal phosphinidene C–H insertion products of benzene and ethylene.…”

The Reaction of Terminal Phosphinidene Complexes [RP–W(CO)5] with Vinylbor­onic Acids: Cycloaddition vs. P–C Bond Formation

“…But this product proved to be rather unstable on standing. (3) When the reaction of [RP-W(CO) 5 ] with vinylboronic acids was run in the presence of K 3 PO 4 , a drastic change of the reaction pathway was observed. The main products of the reaction are now the secondary vinylphosphine complexes 5 [Equation (4)].…”

“…The proposed mechanism involves the insertion of phosphorus into the B-OH bond, followed by the migration of the aryl group from the borate to the phosphorus center. [3] One question immediately arises: Is it possible to transpose this reaction with vinylboronic acids? In this case, of course, the formation of a phosphirane by cycloaddition of the phosphinidene with the C=C double bond [4] can compete with P-C bond formation.…”

Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds

“…Insertion reactions of phosphenium, − phosphide, , and phosphinidene − ligands into transition metal alkyls are enabled by the low coordination and electronic unsaturation of the P fragment. By contrast, well-defined examples of analogous reactions with σ 3 -P ligands have been elusive.…”