First Copper(I) and Silver(I) Complexes Containing Phosphanylphosphido Ligands

Abstract

Three new complexes with phosphanylphosphido ligands, [Cu 4 {μ 2 -P(SiMe 3 )-PtBu} 4 ] (1), [Ag 4 {μ 2 -P(SiMe 3 )-PtBu 2 } 4 ] (2) and [Cu{η 1 -P(SiMe 3 )-PiPr 2 } 2 ] -[Li(Diglyme) 2 ] + (3) were synthesized and structurally characterized by X-ray diffraction, NMR spectroscopy, and elemental analysis. Complexes 1 and 2 were obtained in the reactions of lithium derivative of diphosphane tBu 2 P-P(SiMe 3 )Li·2.7THF with CuCl and [iBu 3 PAgCl] 4 , respectively. The X-ray diffraction analysis

Non‐conventional Behavior of a 2,1‐Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

“…Σ cov (O−Ag)=1.91 Å [20] , see Figures S47). Similar complexes bearing central Ag 4 P 4 cores described in literature mostly contain a charged R 2 P − phosphanide group, but the key structural data are similar for example [Ag 4 (P(NR 2 )C 6 F 5 ) 4 ] [36] , [Ag 4 { cyclo ‐(P 4 t Bu 3 )P t Bu} 4 ] [37] or [Ag 4 (P(P t Bu 2 )SiMe 3 ) 4 ] [38] . In the case of 13 (Figure 8), the phosphorus atom bridges the cobalt atoms with similar P−Co bond lengths 2.118(6) and 2.139(6) Å both being shorter than Σ cov (P−Co)=2.22 Å [20] .…”

Non‐conventional Behavior of a 2,1‐Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

“…Σ cov (OÀ Ag) = 1.91 Å [20] , see Figures S47). Similar complexes bearing central Ag 4 P 4 cores described in literature mostly contain a charged R 2 P À phosphanide group, but the key structural data are similar for example [Ag 4 (P(NR 2 )C 6 F 5 ) 4 ] [36] , [Ag 4 {cyclo-(P 4 tBu 3 )PtBu} 4 ] [37] or [Ag 4 (P(PtBu 2 )SiMe 3 ) 4 ] [38] . In the case of 13 (Figure 8), the phosphorus atom bridges the cobalt atoms with similar PÀ Co bond lengths 2.118(6) and 2.139(6) Å both being shorter than Σ cov (PÀ Co) = 2.22 Å.…”

Cy-clo-tetrakis(μ-diphenylphosphido)-1,5-bis(tri-tert-butylphosphine-tetracopper(I)

“…Treatment of a THF solution of copper(I) chloride with potassium diphenylphosphide in the presence of tri-tert-butylphosphine at -30 °C results in the formation of compound 1 (eq. 1) as determined by single crystal X-ray diffraction, 1 H, 31 P, 13 C NMR, and 31 P HMBC NMR spectroscopy. Compound 1 can also be synthesized by treatment of mesitylcopper(I) with diphenylphosphine in the presence of tri-tert-butylphosphine (eq.…”

“…Compound 1 has been synthesized by three methods and characterized by X-ray diffraction and 1 H, 31 P, 13 C and 31 P HMBC NMR spectroscopy. 1 has been demonstrated to be a hydrophosphination pre-catalyst under photocatalytic conditions.…”

“…H, 31 P,13 C and 31 P HMBC NMR spectra of 1, 1 H and 31 P NMR spectra of a catalytic hydrophosphination experiment, crystallographic information file (CIF) and CheckCIF report for compound 1. Conceptualization, S.D.…”