Showing papers by "Antony J. Deeming published in 1980"
TL;DR: In this paper, a 3-metallated version of the new title ligand (mqp) has been synthesized which contains unidentate, bidentate and 3-measure modes of co-ordination.
Abstract: Complexes of the new title ligand (mqp) have been synthesised which contain unidentate, bidentate, or 3-metallated modes of co-ordination as established by 1H and 13C n.m.r. data. The complex [PdCl2(mqp)2] contains unidentate mqp while [PdCl2(mqp)](as a CH2Cl2 solvate) contains bidentate mqp as shown by a single-crystal structure determination. Crystals are monoclinic, space group P21/c, with a= 12.936(3), b= 13.108(3), c= 15.085(3)A, β= 100.48(2)°, and Z= 4. The structure has been determined by Patterson and Fourier methods and refined by least squares to R 0.047 for 3 490 diffractometer data. In-plane bidentate co-ordination would require a considerable clash of mqp with one cis Cl, but distortions within the still essentially square-planar complex reduce this clash. A small pyramidal distortion at the co-ordinated nitrogen atom contributes to this reduction. This complex yields 3-metallated [Pd2Cl2(mqp-H3)2] in refluxing alcohols in the presence of lithium acetate, but in the absence of the latter the HCl formed leads to the quinolinium salt of the 3-metallated product. Various chlorocarbonyl derivatives of [Rh2Cl2(CO)4] are described, the most significant being [Rh2Cl2(CO)3(mqp)] which contains bidentate mqp and shows nuclear spin–spin coupling between the nuclei of the 8-Me group and the 103Rh and 31P nuclei, indicating a significant interaction between the non-metallated Me group and the metal atom. 3-Metallated mqp complexes of iridium(III) and of manganese(I) are also described.
16 citations
TL;DR: In this paper, a complex [Rh(CO)-PPh3)2L][ClO4] was constructed from [Rh2Cl2(CO)4] by adding unidentate L (8-methyl-, -ethyl-, or -isopropyl-quinoline) or bidentate l (1,10-phenanthroline or quinoline-2-carboxaldehyde-N-methylimine).
Abstract: The complexes [Rh(CO)(PPh3)2L][ClO4] have been prepared from [Rh(CO)(PPh3)2(CH3COCH3)][ClO4] on adding unidentate L (8-methyl-, -ethyl-, or -isopropyl-quinoline) or bidentate L (1,10-phenanthroline or quinoline-2-carboxaldehyde-N-methylimine). 8-Alkyl-substitution of the latter ligand gives the complexes [Rh(CO)-(PPh3)2L][ClO4] as isomers with uni- and bi-dentate L respectively with relative stabilities of the unidentate form depending on the 8-substituent in the order Pri > Et > Me. Unidentate L is also favoured by replacing PPh3 by P(C6H11)3, but bidentate co-ordination is found using AsPh3 or PMe2Ph. Equilibrium constants for chlorobridge cleavage of [Rh2Cl2(CO)4] by 8-substituted and 2,8-disubstituted quinolines are reduced by increasing the size of the 8-substituent and even more by further introduction of a 2-methyl group. The contributions of distortions in the co-ordination to these changes in equilibrium constants are discussed.
11 citations
TL;DR: The diastereomers of [HOs3(CO)10(µ-PhCHMeNHCO] have been separated by t.m.l.c.r. and c.d.
Abstract: Enantiomers of [HOs3(CO)10(µ-PhCH2NHCO)] interconvert slowly on an n.m.r. time-scale and diastereomers of [HOs3(CO)10(µ-PhCHMeNHCO)] have been separated by t.l.c. and characterised by their 1H n.m.r. and c.d. spectra.
10 citations
TL;DR: In this article, a carbon-carbon σ-bond is cleaved in the reaction of the diols HOCR2CCCR2OH (R = Me or Ph) with the osmium or ruthenium carbonyls [M3(CO)12] to give [HM3( CO)9(CCR2OH)], a reaction which appears to be generally applicable to α-hydroxyalkynes not containing an α- hydrogen atom.
Abstract: A carbon–carbon σ-bond is cleaved in the reaction of the diols HOCR2CCCR2OH (R = Me or Ph) with the osmium or ruthenium carbonyls [M3(CO)12] to give [HM3(CO)9(CCR2OH)], a reaction which appears to be generally applicable to α-hydroxyalkynes not containing an α-hydrogen atom.
9 citations
TL;DR: In this paper, it was shown that N -Benzyl-2-aminopyridine gives isomers analogous to each of these clusters, the difference being in the ability of the benzyl group to be ortho-metallated.
6 citations