Aminophosphine Complexes

Deh, Marcus Kwaku (1977) Aminophosphine Complexes. PhD thesis, University of Glasgow.

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Aminophosphine complexes with the empirical formulae Mx2P(NMe2)3 (M = Zn, Hg, X = Cl, Br, I; M = Cd, X = Cl), MX 2P(NMe2)3 (M=Hg, X=Cl,Br,I; M = Zn, Cd, X = Cl) and tris(2-pyridyl)phosphine complexes MX2Py3P (M = Zn, Hg, X = Cl,Br, I) and MX (Py3P)2 (M=Pt, X=Cl) have been reinvestigated. The mode of co-ordination in the complexes were studied using i. r, Raman and n. m. r. (1H, 31P, 13C, 199Hg) spectroscopy. The new complexes HgCl2PhP(NMe2)2, PtI2(Py3P)2 and (MX2 Py3PS (M = Zn, Hg, X=Cl,Br,I) were prepared and studied. I. r. spectra in the P-N region indicate that the MX2 P(NMe2)3 and WX22P(NMe2)3 complexes are co-ordinated through the phosphorus atoms. Far i. r. spectra (400-40 cm -1) indicate that the MX2P(NMe2)3 complexes are dimeric with bridging halogens. The MX2P(NMe2)3 complexes show one or two metal-halogen stretching frequencies consistent with M(II) ions in pseudo-tetrahedral environments. Assignments are made for dimeric trans-symmetrical cis-symmetrical and unsymmetrical species in CDCl3 solution of ZnCl2P(NMe2)3 on the basis of 1H, 31P, and 13C n. m. r. spectra. Variable temperature 1H n. m. r. studies on HgX22P(NMe2)3 indicate a fast exchange of phosphorus ligands. The order of the rate of phosphorus ligand exchange is I > Br > Cl 1H - {199Hg} INDOR spectrum of HgCl2P(NMe 2)3 indicate one phosphine ligand bonded to Hg(II), 199Hg decoupling experiments on the 1H spectrum of HgCl22P(NMe2)3 indicate two phosphine ligands bonded to Hg(II). One-bond 199Hg-31P nuclear spin coupling constants for HgX2P(NMe2)3 (X=Cl, Br), HgCl22P(NMe2)3 and HgCl2PhP(NMe2)2 are in the range of directly bonded 199Hg-31P couplings. I. r. Spectra in the regions 1600-1550 and 700-600 cm-1 indigate that in the ZnX2Py3P and ZnX2y3PS complexes the three pyridyl nitrogen atoms are co-ordinated to Zn(II). I. r. Spectra in the P→S region indicate the presence of Hg-S bonds in the HgX2Py3PS complexes. Far i. r. Spectra (400-40 cm-1) indicate that ZnX2Py3P and ZnX2y3PS are dimeric with Zn(II) in 6-co-ordinate pseudo-octahedral environments. HgX2y3PS complexes are also dimeric with Hg(II) in pseudo-tetrahedral environments. A trans-symmetrical structure is proposed for HgX2P3PS and HgX2Py3P complexes. The one bond C-P nuclear spin coupling constants for HgX2Py3P complexes in DMSO-d6 solution increased relative to the free ligand denoting a substantial change in phosphorus hybridization on co-ordination of phosphorus and hence the presence of a Hg-P bond. Two very strong absorptions at 324 and 300 cm-1 for PtCl2(Py3P)2 are correlated with Pt-Cl stretches for a cis-Pt(II) halide complex, 1J(195Pt-31P) for PtCl2(PyP)2 is consistent with the presence of a Pt-P bond.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1977
Depositing User: Enlighten Team
Unique ID: glathesis:1977-78755
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 30 Jan 2020 14:56
Last Modified: 30 Jan 2020 14:56

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