REACTION OF PHENYL AND METHYL DISULFIDE WITH CENTER-DOT-CR(CO)(3)C(5)ME(5) AND HCR(CO)(3)C(5)ME(5) - METAL RADICAL AND METAL HYDRIDE REACTIVITY AT THE SULFUR-SULFUR BOND - DIFFERENT MECHANISMS FOR OXIDATIVE ADDITION OF ALKYL AND ARYL DISULFIDES
Td. Ju et al., REACTION OF PHENYL AND METHYL DISULFIDE WITH CENTER-DOT-CR(CO)(3)C(5)ME(5) AND HCR(CO)(3)C(5)ME(5) - METAL RADICAL AND METAL HYDRIDE REACTIVITY AT THE SULFUR-SULFUR BOND - DIFFERENT MECHANISMS FOR OXIDATIVE ADDITION OF ALKYL AND ARYL DISULFIDES, Inorganic chemistry, 36(4), 1997, pp. 614-621
The enthalpies of reaction of the . Cr(CO)(3)C(5)Me(5) and disulfides
(RSSR) forming RS-Cr(CO)(3)C(5)Me(5) have been measured by solution ca
lorimetry, Delta H = -13.3 + 1.5 kcal/mol (R = Ph) and -11.2 + 1.2 kca
l/mol (R = Me). These data lead to Cr-SR bond strength estimates of 35
and 43 kcal/mol, respectively. The rates of oxidative addition have b
een investigated by FTIR spectroscopy. Phenyl disulfide reacts by a se
cond-order mechanism whose rate-determining step is the attack of the
chromium radical on the sulfur-sulfur bond, yielding chromium thiolate
and a thiyl radical [k(298 K) 1.3 M(-1) s(-1), Delta H-phi = +10.2 kc
al/mol, Delta S-phi = -24.4 cal/(mol deg)]. Methyl disulfide reacts by
a third-order mechanism going through a termolecular transition state
in which the stronger sulfur-sulfur bond in the alkyl disulfide is at
tacked simultaneously by two chromium radicals [k(298 K = 393 M(-2) s(
-1), Delta H-phi = -0.2 kcal/mol, Delta S-phi = -47 cal/(mol deg)]. Th
e rates of reaction of MeSSMe and PhSSPh with the hydride H-Cr(CO)(3)C
(5)Me(5) have also been investigated in the presence of varying amount
s of added . Cr(CO)(3)C(5)Me(5) radical. MeSSMe shows no apparent reac
tion with HCr(CO)(3)C(5)Me(5), even in the presence of added . Cr(CO)(
3)C(5)Me(5). PhSSPh reacts with HCr(CO)(3)C(5)Me(5) primarily by a rad
ical chain process involving . Cr(CO)(3)C(5)Me(5) and PhS . radicals.
The upper limit to the rate of reaction by nonradical concerted additi
on is k(obs) < 4 x 10(-4) M(-1) s(-1).