Gillian W. Harris

Synthesis and crystal structure of t-butylisocyanidenonacarbnyldirhenium(0): Re2(CO)9(CNBut)

Abstract The compound Re2(CO)9(CNBut) was synthesized in high yield by the PdO catalysed reaction between Re2(CO)10 and ButNC. The molecular structure of this complex has been determined by X-ray crystallography: Space group: Pbca, a 17.160(7), b 18.300(7), c 12.370(b) A, V 3884.53 A3, Z = 8, R = 0.0994. The structure of the dimer has a staggered configuration with the isonitrile ligand occupying an equatorial position.

Catalytic synthesis of (η5-C5H5)Mn(CO)2(CNR) complexes and the crystal and molecular structure of (η5-C5H5)Mn(CO)2,(CNBut)

Abstract The complexes (η 5 -C 5 H 5 )Mn(CO) 2 (CNR) (R= Bu t , C 6 H 5 CH 2 , C 6 H 11 , C 6 H 3 Me 2 -2,6, Me) are synthesized by the PdO catalysed thermal reaction between (η 5 -C 5 H 5 )Mn(CO) 3 and RNC. The crystal and molecular structure of (η 5 C 5 H 5 )Mn(CO) 2 (CNBu t ) has been determined by single crystal X-ray diffraction. In this structure the isonitrile ligand is bent away from the ring with a CNC angle of 172(2)°.

Synthesis and characterisation of a series of vanadium isonitrile complexes

Abstract The reaction between (η 5 -C 5 H 5 )V(CO) 4 and RNC in the presence of PdO as catalyst to give (η 5 -C 5 H 5 )V(CO) 4 − n (CNR) n ( n = 1–3) is reported. The complexes have been characterized by IR and 51 V and 1 H NMR spectroscopy.

Relating infra red spectral data to structure for a series of M2(CO)10−n(L)n complexes (M=Re, Mn; L=CNR, PR3; R=Alkyl, Aryl; n=1−4)

An analysis of the IR spectral patterns of a series ofM2(CO)10−n(L)n complexes (whereM=Re, Mn; L=CNR, PR3;R=Alkyl, Aryl;n=1−3), taking as far as possible example structures that have been determined by X-ray crystallography, has enabled a correlation to be established between the number and intensity ofv(CO) IR bands and the substitution geometry of the complex. Such a set of standard IR spectral patterns can be used as an easy means of verifying the substitution geometry of such complexes.

The palladium-catalysed reaction between [Re2(CO)10] and phosphines and the crystal and molecular structure of diaxial [Re2(CO)8(PMe2Ph)2]

The reaction between [Re2(CO)10] and PR3[PR3= PPh3, PMePh2, PMe2Ph, PMe3, P(CH2Ph)3, or P(OMe)3] in xylene is catalysed by Pd/C, Pd/CaCO3, and PdO and yields the complexes [Re2(CO)10–n(PR3)n](n=1 or 2) as the major products (15–80%). Attempts to synthesise [Re2(CO)10–n(PR3)n] from [Re2(CO)10] and PR3in the presence of NMe3O under milder conditions (e.g. refluxing CH2Cl2) also gave the above products with n=1 or 2 as well as high yields of fac[ReCl(CO)3(PR3)2]. An X-ray crystal structure determination of diaxial [Re2(CO)8(PMe2Ph)2] was carried out: space group C2/c, Z= 4, a= 22.779(9), b= 7.1 66(3), c= 17.249(7)A, β= 95.13(3)°, R= 0.0602. The structure has a staggered geometry with torsion angles deviating by ± 6° from the ideal (45°). The Re–Re bond length was found to be 3.044(1)A, cf., 3.041(1)A for [Re2(CO)10], indicating that this parameter is almost invariant on substitution of CO by PMe2Ph.

A structural and kinetic investigation of the isomers of M2(CO)8(CNBut)2 (M=Mn, Re)

The kinetic product of the catalysed reaction between Mn2(CO)10 and ButNC, 1, 2-Mn2(CO)8(CNBut)2, isomerizes on heating to the 1,1 isomer which has been characterized by X-ray crystallography.