Enhanced thermal stability of Cu–silylphosphido complexes via NHC ligation

Abstract

The facile preparation and structural characterization of [M6{P(SiMe3)2}6] (M = Ag, Cu) is reported. These complexes show limited stability towards solvent loss at ambient temperature; however, N-heterocyclic carbene (NHC) ligands were used to synthesize more thermally stable metal-silylphosphido compounds. 1,3-Di-isopropylbenzimidazole-2-ylidene ((i)Pr2-bimy) and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) are found to be excellent ligands to stabilize silylphosphido-copper compounds that show higher stability when compared to [Cu6{P(SiMe3)2}6].

Structural, Spectroscopic, and Computational Analysis of Heterometallic Thorium Phosphinidiide Complexes

“…The Cu–phosphido distances Cu1–P2, Cu1–P3, Cu3–P3, and Cu3–P4 of 2.295(2), 2.31(1), 2.28(1), and 2.291(2) Å, respectively, are nearly identical with the Cu–phosphinidiide bond lengths Cu1–P1, Cu2–P1, Cu2–P5, and Cu3–P5 of 2.302(2), 2.228(2), 2.238(2), and 2.291(2) Å, respectively. These distances are similar to those in reported copper­(I) phosphido complexes. , The Th1–Cu1 and Th2–Cu3 bond distances of 3.1885(9) and 3.2337(8) Å are only slightly longer than those observed previously by Zi, Ding, Walter, and co-workers of 3.140(1)–3.171(1) Å and still shorter than the sum of the covalent radii of 3.38 Å . The only other actinide–coinage metal bond reported is U IV –Ag I with a distance of 3.1533(6) Å .…”

Copper–Phosphido Intermediates in Cu(IPr)-Catalyzed Synthesis of 1-Phosphapyracenes via Tandem Alkylation/Arylation of Primary Phosphines

“…NMR spectra were obtained in CD 2 Cl 2 , although slow decomposition was observed in solution. 7.21 (apparent t, J = 7, 2H), 7.11 (broad, d, J = 6, 1H), 6.98 (broad, d, J = 6, 1H), 6.79 (broad, 2H), 6.73 (broad, 1H), 4.88 (broad, d, J = 344, P−H), 4.11 (broad, d, J = 11, 1H, benzyl-CH 2 ), 3.66 (broad, 1H, benzyl-CH 2 ), 3.31 (4H, ace-CH 2 ), 2.52 (sept, J = 7, 4H, CH), 1.21 (d, J = 7, 12H, CH 3 ), 1.08 (broad, 12H, CH 3 ).…”

“…However, little is known about the key proposed intermediates, monomeric terminal copper phosphido complexes Chart shows the only directly observed catalytically relevant terminal Cu–phosphido intermediates, A and B , , and the only isolated complexes, C and D . − The P-stereogenic derivatives L n Cu­(PRR′), potential intermediates in catalytic asymmetric synthesis of chiral phosphines, have not yet been reported.…”

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

“…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].…”