Solid-state sup 31 P NMR, far-IR, and structural studies on two-coordinate (tris(2,4,6-trimethoxyphenyl)phosphine)copper(I) chloride and bromide

Journal Article · Wed Apr 19 00:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00307a009· OSTI ID:5062846

Bowmaker, G A ^[1]; Cotton, J D ^[2]; Healy, P C ^[3]; Silong, S B ^[4]; Kildea, J D; Skelton, B W; White, A H ^[5]

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1. Univ. of Auckland (New Zealand)
2. Univ. of Queensland, Brisbane (Australia)
3. Griffith Univ., Brisbane (Australia)
4. Universiti Pertanian Malaysia, Serdang (Malaysia)
5. Univ. of Western Australia, Perth (Australia)

The reactions of acetonitrile solutions of copper(I) chloride, CuCl, and copper(I) bromide, CuBr, with the sterically hindered, highly basic tertiary phosphine ligand tris(2,4,6-trimethoxyphenyl)phosphine ({equivalent to}P(2,4,6){sub 3}) have been shown to form 1:1 monomeric adducts, (P(2,4,5){sub 3}CuX). The two compounds are isomorphous, crystallizing in the tetragonal space group P4{sub 3}. For the chloride, a = 15.237 (4) {angstrom}, c = 12.373 (3) {angstrom}, Z = 4, and R = 0.029 for 2339 observed (I {ge} 3{sigma}(I)) reflections, while for the bromide, a = 15.312 (8) {angstrom}, c = 12.457 (6) {angstrom}, Z = 4, and R = 0.052 for 2148 observed reflections. Cu-P is 2.177 (1) {angstrom} and Cu-Cl is 2.118 (2) {angstrom} in the chloro compound; for the bromide, Cu-P is 2.197 (3) {angstrom} and Cu-Br is 2.259 (2) {angstrom}. In both complexes, the copper atom is displaced toward the nearest o-methoxy oxygen with Cu{hor ellipsis}O = 2.629 (4) (Cl) and 2.628 (7) {angstrom} (Br); P-Cu-X angles are 172.97 (6) (Cl) and 172.00 (9){degree} (Br). Far-infrared spectra show expected strong {nu}(Cu-Cl) and {nu}(Cu-Br) bands at 355 and 262 cm{sup {minus}1}, respectively. Strong bands in the range 90-100 cm{sup {minus}1} are assigned to {delta}(P-Cu-X) bending modes. No bands assignable to {nu}(Cu-P) modes were observable. The solid-state {sup 31}P NMR spectrum of the ligand is characterized by a single line at -73 ppm (with respect to 85% H{sub 3}PO{sub 4}). The spectrum for each complex shows an asymmetric quartet centered at -65 ppm with highly asymmetric line spacings of 1.40, 2.21, and 2.50 kHz and 1.48, 2.17, and 2.43 kHz, respectively. These data have been used to estimate copper nuclear quadrupole coupling constants for the two compounds. 20 refs., 5 figs., 4 tabs.

• OSTI ID: 5062846
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:8; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AROMATICS
CRYSTAL STRUCTURE
COPPER BROMIDES
COPPER CHLORIDES
ORGANIC OXYGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHINES
CHEMICAL PREPARATION
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
NMR SPECTRA
PHOSPHORUS 31
BROMIDES
BROMINE COMPOUNDS
CHLORIDES
CHLORINE COMPOUNDS
COPPER COMPOUNDS
COPPER HALIDES
DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation