EPR-SPECTRA OF THE COMPLEXES OF P(OME)3 AND PME3 WITH CU ATOMS IN HYDROCARBON MATRICES AT 77-K

被引：2

作者：

HISTED, M ^{[1
]}

HOWARD, JA ^{[1
]}

JOLY, HA ^{[1
]}

MILE, B ^{[1
]}

机构：

[1] UNIV COLL CARDIFF,COLL CARDIFF,SCH CHEM & APPL CHEM,CARDIFF CF1 3TB,WALES

来源：

CHEMICAL PHYSICS LETTERS | 1990年 / 174卷 / 05期

关键词：

D O I：

10.1016/S0009-2614(90)87171-M

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The paramagnetic products from reacting Cu atoms with P(OMe)3 and PMe3 on a rotating cryostat have been examined by EPR spectroscopy and shown to be mainly the seventeen-electron tris(trivalent phosphorus) complexes, Cu[PX3]3. Their magnetic parameters are consistent with a planar π radical structure in D3h symmetry. The Cu undergoes sp2 hybridization with the phosphorus ligands donating their lone-pair electrons into these three empty orbitals and the unpaired electron occupying mainly the remaining Cu 4pz orbital perpendicular to the molecular plane. There is less back donation of unpaired spin population into P σ* or 3d orbitals than there is into the π* orbitals of CO in the isostructural carbonyl complex, Cu(CO)3. © 1990.

引用

页码：411 / 415

页数：5

共 30 条

[1]

Howard, Mile, Morton, Preston, Sutcliffe, Chem. Phys. Letters, 117, (1985)

[2]

Howard, Mile, Morton, Preston, Sutcliffe, J. Phys. Chem., 90, (1986)

[3]

Howard, Mile, Morton, Preston, J. Phys. Chem., 90, (1986)

[4]

Chenier, Hampson, Howard, Mile, J. Phys. Chem., 93, (1989)

[5]

Kasai, Jones, J. Am. Chem. Soc., 107, (1985)

[6]

Malatesta, Cenini, Zero valent compounds of metals, (1974)

[7]

Paulik, RECENT DEVELOPMENTS IN HYDROFORMYLATION CATALYSIS, Catalysis Reviews, 6, (1972)

[8]

Whyman, Transition metal complexes, (1980)

[9]

McAuliffe, Transition metal complexes of phosphorus, arsenic and antimony ligands, (1973)

[10]

Tolman, Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis, Chemical Reviews, 77, (1977)

← 1 2 3 →