publication . Thesis

Isolation, characterisation and reactivity of five-coordinate PtIV complexes.

Shaw, Paul Anthony;
Open Access English
  • Country: United Kingdom
Abstract
The oxidative addition to square planar dicyclometallated C^N^C PtII 16 valence electron complexes (C^N^C= 2,6-di(4-fluorophenyl)pyridine and 2-(4-fluorophenyl)-6-tertbutylpyridine) was studied with Cl2 (via PhICl2) and alkyl halides (e.g. MeI, BnBr and allylBr). The two-step nature of the process meant that PtIV 16 valence electron fivecoordinateintermediates could be identified. The product of oxidation was an octahedral 18 valence electron product with the new groups added mutually trans across the metal, with isomerisation seen with time. However, in the case of the chlorine-based oxidant, PhICl2, this was only part of the story, where further reactivity dep...
Subjects
free text keywords: QD
Related Organizations
101 references, page 1 of 7

Youngs and M. R. Churchill, J. Am. Chem. Soc., 1978, 99, 5962-5964.

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M. P. Brown, R. J. Puddephatt and C. E. E. Upton, J. Chem. Soc. Dalton Trans., 1974, 22, 2457-2465.

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N. Miyaura, K. Yamada and A. Suzuki, Tetrahedron Lett., 1979, 20, 3437-3440.

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101 references, page 1 of 7
Abstract
The oxidative addition to square planar dicyclometallated C^N^C PtII 16 valence electron complexes (C^N^C= 2,6-di(4-fluorophenyl)pyridine and 2-(4-fluorophenyl)-6-tertbutylpyridine) was studied with Cl2 (via PhICl2) and alkyl halides (e.g. MeI, BnBr and allylBr). The two-step nature of the process meant that PtIV 16 valence electron fivecoordinateintermediates could be identified. The product of oxidation was an octahedral 18 valence electron product with the new groups added mutually trans across the metal, with isomerisation seen with time. However, in the case of the chlorine-based oxidant, PhICl2, this was only part of the story, where further reactivity dep...
Subjects
free text keywords: QD
Related Organizations
101 references, page 1 of 7

Youngs and M. R. Churchill, J. Am. Chem. Soc., 1978, 99, 5962-5964.

R. R. Schrock, J. Am. Chem. Soc., 1976, 98, 5399-5400.

Chem. Int. Ed., 1973, 85, 618-620.

W. C. Zeise, Annu. Rev. Phys. Chem., 1831, 97, 497.

G. Stephan, C. N̈ther, G. Peters and F. Tuczek, Inorg. Chem., 2013, 52, 5931- 5942.

G. B. Kauffman, J. Chem. Educ., 1983, 60, 185-186.

T. J. Kealy and P. L. Paulson, Nature, 1951, 168, 1039-1040.

J. D. Dunitz and L. E. Orgel, Nature, 1953, 171, 121-122.

Akutagawa, J. Am. Chem. Soc., 1987, 109, 5856-5858.

J. A. Labinger, Organometallics, 2015, 34, 4784-4795.

J. Halpern, Acc. Chem. Res., 1970, 3, 386-392.

M. P. Brown, R. J. Puddephatt and C. E. E. Upton, J. Chem. Soc. Dalton Trans., 1974, 22, 2457-2465.

J. F. Hartwig, Organotransition Metal Chemistry: From Bonding to Catalysis, University Science Books, Mill Valley, California, 2009.

N. Miyaura, K. Yamada and A. Suzuki, Tetrahedron Lett., 1979, 20, 3437-3440.

A. Suzuki, Angew. Chem. Int. Ed., 2011, 50, 6723-6733.

101 references, page 1 of 7
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