A dynamic NMR study of sulphur inversion in transition metal complexes of 2,6-dithiaspiro[3.3]heptane (2,6-DTSH), 2,6-DTSH-2-oxide and 2,6-DTSH-2,2-dioxide

Autor:	Edward W. Abel, Mark C. Poole, Keith G. Orrell, Vladimir Šik
Rok vydání:	1999
Předmět:	Heptane Inorganic chemistry Oxide chemistry.chemical_element Tungsten Sulfur Inorganic Chemistry chemistry.chemical_compound Transition metal chemistry Atom Materials Chemistry Physical chemistry Physical and Theoretical Chemistry Lone pair Palladium
Zdroj:	Polyhedron. 18:1345-1353
ISSN:	0277-5387
DOI:	10.1016/s0277-5387(98)00445-8
Popis:	The following complexes were synthesised [W(CO)5L1], [{W(CO)5}2L1], [W(CO)5L2], [W(CO)5L3], [{PdCl2(PPh3)}2L1], [PdCl2(PPh3)L2] and [PdCl2(PPh3)L3] where L1=2,6-dithiaspiro[3.3]heptane (2,6-DTSH), L2=2,6-DTSH-2-oxide and L3=2,6-DTSH-2,2′-dioxide. In solution these complexes exhibit pyramidal inversion of the metal-coordinated sulphur atom(s), rates and activation energies of which were evaluated by total NMR bandshape analysis. ΔG‡ values were in the range 45–50 kJ mol−1. These magnitudes are discussed in terms of ring geometry distortions and sulphur lone pair interactions.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::6a00c713d5d5c2c64394ceab0c81574a https://doi.org/10.1016/s0277-5387(98)00445-8 Zobrazit plný text záznamu Full Text from ScienceDirect