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Oxidative addition of thiols to a coordinatively unsaturated triplatinum cluster complex

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00296a040· OSTI ID:5775669
;
Reaction of RSH with (Pt/sub 3/(/mu//sub 3/-CO)(/mu/-dppm)/sub 3/)(PF/sub 6/)/sub 2/ (1, dppm = Ph/sub 2/PCH/sub 2/PPh/sub 2/) gave CO and (Pt/sub 3/H(/mu//sub 3/-SR)(/mu/-dppm)/sub 3/)(PF/sub 6/)/sub 2/ 2a, R = Me; 2b, R = Et; 2c, R = CH/sub 2/Ph; 2d, R = CH/sub 2/CO/sub 2/Et; 2e, R = Ph; 2f, R = 4-MeC/sub 6/H/sub 4/ and, when R = aryl, (Pt/sub 3/(SR)(/mu//sub 3/-SR)(/mu/-dppm)/sub 3/)(PF/sub 6/)/sub 2/ (3a, R = Ph; 3b, R = 4-MeC/sub 6/H/sub 4/). Reaction of t-BuSH with 1 gave the known complex (Pt/sub 3/H(/mu//sub 3/-S)(/mu/-dppm)/sub 3/)(PF/sub 6/) (4). Mixed-thiolate derivatives Pt/sub 3/(SR)(/mu//sub 3/-SR')(/mu/-dppm)/sub 3/(PF/sub 6/)/sub 2/ (3c, R = Me, R' = Ph; 3d, R = Ph, R' = Me) were formed by reaction of 2a with PhSH. In some cases, thiolate-exchange reactions were observed; for example, 2e with excess MeSH gave mostly 2a. PhSeH reacted with 1 to give a mixture of (Pt/sub 3/H(/mu//sub 3/-SePh)(/mu/-dppm)/sub 3/)(PF/sub 6/)/sub 2/ (5) and (Pt/sub 3/(SePh)(/mu//sub 3/-SePh)(/mu/-dppm)/sub 3/)(PF/sub 6/)/sub 2/ (6). In the reactions of 1 with EtSH or PhSH, low-temperature /sup 31/P and /sup 13/C NMR experiments showed the formation of a rapid preequilibrium between the reagents and (Pt/sub 3/(/mu//sub 3/-CO)(RSH)(/mu/-dppm)/sub 3/)/sup 2+/ (7a, R = Et; 7b, R = Ph). These reacted further to give 2b or 2e on warming to /approx/ 0/degree/C. PhSeH gave the analogous intermediate (Pt/sub 3/(/mu//3/-CO)(PhSeH)(/mu/-dppm)/sub 3/)/sup 2+/ and, with excess PhSeH, another species, which is probably (Pt/sub 3/H/sub 2/(/mu/-SePh)(/mu/-dppm)/sub 3/)/sup 3+/. 10 refs., 3 figs., 2 tabs.
Research Organization:
Univ. of Western Ontario, London (Canada)
OSTI ID:
5775669
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:23; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS FLUORIDES
PLATINUM COMPLEXES
THIOLS
TRANSITION ELEMENT COMPLEXES