Synthesis and X‐ray Structural Characterization of (Diisopropylamino)(Morpholino)(Phenyl)Phosphine and its Dimeric Copper(I)

Abstract

An electron rich “hybrid” asymmetric aminophosphine, (diisopropylamino)(morpholino) (phenyl)phosphine, L, was synthesized in good yield by step‐wise aminolysis reactions with dichloro(phenyl)phosphine and structurally characterized. The complex, CuCl(L) was readily isolated from both 1∶1 and 1∶2 reactions of L with CuCl. Single crystal X‐ray structures of L and two copper complexes, [CuCl(L) · CH₃CN]₂ (1) and [CuCl(L) · CH₂Cl₂]₂ (2) have been determined. X‐ray structures reveal pyramidal nature of phosphorus and near planar geometry of nitrogen of the phosphine ligand and the dimeric nature of the complexes with tricoordinate copper(I) centers. The asymmetric phosphine crystallizes in monoclinic system with space group P21/c and unit cell dimensions as a=17.219(1) Å, b=13.469(1) Å, c=7.395(5) Å, α=90.00°, β=93.11(1)°, γ=90.00°. Both acetonitrile (1) and dichloromethane (2) solvates crystallize in triclinic system with space group Pī. The unit cell dimensions of (1) are a=10.143(2) Å, b=13.681(3) Å, c=16.647(3) Å, α=83.14(1)°, β=76.91(1)°, γ=68.83(1)° and that of (2) are a=8.899(1) Å, b=11.727(1) Å, c=11.784(1) Å. α=66.73(1)°, β=82.27(1)°, γ=84.04(1)°. This is the first report of copper(I) phosphine complexes in which the coordinated asymmetric phosphine carries two different amino substituents.

Keywords:

• aminophosphine
• copper(I) complex
• synthesis
• x‐ray structures
• tri‐coordinate copper

Acknowledgments

T. A. L thanks IIT Madras for a research fellowship. Sophisticated Analytical Instruments Facility, IIT Madras is acknowledged for XRD and spectral facilities.

Dedicated to Prof. Herbert W. Roesky, Institute for Inorganic Chemistry, Göttingen, Germany, on his 70th birthday.