The first ring-expanded NHC–copper(i) phosphides as catalysts in the highly selective hydrophosphination of isocyanates

Abstract

A range of N-heterocyclic carbene-supported copper diphenylphosphides (NHC = IPr, 6-Dipp, SIMes and 6-Mes) were synthesised. These include the first reports of ring-expanded NHC-copper(I) phosphides. The compounds were characterised by...

Cyclo-Tetrakis(μ-diphenylphosphido)-1,5-bis(tri-tert-butylphosphine)-Tetracopper

“…The influence of the electron-rich P t Bu 3 manifests in the increased bond length between Cu1 and P1 (2.3076 (10) Å) versus that of Cu2 and P1 (2.2.2272 (12) Å) (Table 1). Both values are within the range of previously reported µ 2-Cu-P bonds [5,17]. The closest copper-copper distances are between Cu2 and Cu4, (2.8612(13)), which is larger than the sum of covalent radii (2.64 Å) [8].…”

“…Metal phosphido compounds are important synthetic intermediates in organophosphorus chemistry [1][2][3]. Most copper phosphido compounds characterized by X-ray crystallography have oligomeric structures [4][5][6][7][8][9][10][11][12][13][14][15] with a few notable exceptions [16,17]. We have been studying these types of compounds as intermediates in copper catalyzed hydrophosphination [18].…”

Catalytic Hydrophosphination of Isocyanates by Molecular Antimony Phosphanides

“…The catalytic hydrophosphination of carbodiimides (RN=C=NR) has been demonstrated with compounds of potassium, [15] and the alkaline earth metals (Ca, Sr and Ba), [16] whilst the corresponding reactions with isocyanates (RN=C=O) is restricted to metal compounds of the d ‐block (Zr, [17] Fe, [18] Cu, [19] Zn [20] ) and f ‐block (La, [21] U, [22] Th [22–23] ). In this context we previously examined the potential for bismuth phosphanides Bi(NON R )(PR′ 2 ) (NON R =[O(SiMe 2 NR) 2 ] 2− ; R=Dipp=2,6‐ i Pr 2 C 6 H 3 , t Bu; R′=Ph, Cy) to undergo hydrophosphination‐type reactivity with isocyanates (Scheme 1).…”

An efficient catalytic method for hydrophosphination of heterocumulenes with diethylzinc as precatalyst without a solvent

“…So far, many transition metal-catalyzed reactions have been reported, such as the addition of phosphine oxide to CvC and CuC bonds. [30][31][32][33][34][35][36] Furthermore, a number of metal catalysts have been investigated and reported involving organic alkali metal compounds, 37 heavier group 2 complexes, 38 Rare-Earth-metal complexes, [39][40][41] and late transition metal compounds 42,43 to promote the addition of the phosphines P-H to carbodiimides, isocyanates, and isothiocyanates.…”