Structural and 31P CP MAS NMR Spectroscopic Studies of the P2CuN2 copper(I) complexes [Cu(PPh3)2(MeCN)2]X for X = PF6,BF4 and CI04

No Thumbnail Available
File version
Author(s)
Hanna, JV
Hart, RD
Healy, PC
Skelton, BW
White, AH
Griffith University Author(s)
Primary Supervisor
Other Supervisors
Editor(s)
Date
1998
Size
File type(s)
Location
License
Abstract

The mixed ligand P2CuN2 copper(I) complexes [Cu(PPh3)2(MeCN)2]X have been studied by one- and two-dimensional 31P CP MAS NMR spectroscopy for X = PF6, BF4 or ClO4 and single crystal X-ray diffraction for X = PF6 and ClO4, completing availability of precise structural data for this isomorphous series. The compounds crystallise as discrete cations and anions in space group P21/n with a 15, b 27, c 9 , = 95ଠZ = 4. The anion is located ca. 6 from the copper atom and adjacent to a cleft formed between the acetonitrile ligands and phosphine ligand 2 while the crystallographically independent PPh3 ligands adopt staggered three-bladed propeller-type conformations of opposite chirality. The geometric symmetry of the P2CuN2 co-ordination sphere is low with Cu-P(1) 2.276(4)-2.287(2), Cu-P(2) 2.258(4)-2.269(1) , Cu-N 2.023(9)-2.053(3) , P-Cu-P 126.82(4)-127.73(5), N-Cu-N 99.5(4)-100.3(1), P(1)-Cu-N 100.87(8)-102.34(9) and P(2)-Cu-N 110.4(1)-111.9(3)஠One- and two-dimensional solid state 31P CP MAS NMR spectra of the compounds at 9.40 T show chemical shift differences of 6 ppm between the signals arising from the two P sites which form part of an ABX spin system with 1J[31P(1)-63Cu] 1.13-1.14 kHz, 1J[31P(2)-63Cu] 1.30 kHz and 2J(31P-31P) 75 Hz. The copper quadrupolar induced distortion of the line spacings is different for the two sites and is postulated to be a consequence of variation in the angle between the Cu-P vectors and the z axis of the electric field gradient tensor. The magnitude of the distortion is relatively small and consistent with small copper quadrupolar coupling constants for the compounds and a balanced electronic charge distribution about the copper(I) site in spite of the low geometric symmetry of the P2CuN2 co-ordination sphere.

Journal Title
Journal of the Chemical Society. Dalton Transactions
Conference Title
Book Title
Edition
Volume
Issue
Thesis Type
Degree Program
School
Patent number
Funder(s)
Grant identifier(s)
Rights Statement
Rights Statement
© 1998 Royal Society of Chemistry. Please refer to the journal link for access to the definitive, published version.
Item Access Status
Note
Access the data
Related item(s)
Subject
Inorganic Chemistry
Other Chemical Sciences
Theoretical and Computational Chemistry
Persistent link to this record
Citation
Collections