Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume -, Issue 30, Pages 4790-4800Publisher
WILEY-BLACKWELL
DOI: 10.1002/ejic.201000503
Keywords
Osmium; Pincer; Oxygen reduction; Hydrogen; C-H bond cleavage
Categories
Funding
- National Science Foundation (NSF) [NSF-CHF-0544829]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0749386] Funding Source: National Science Foundation
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A synthesis of [(PNP)OsI] {PNP = (tBu(2)PCH(2)SiMe(2))(2)N} permits evaluation of its reactivity, both Lewis acidity and reducing power (i.e., ability to be oxidized). It binds two molecules of PhCN, into trans sites, but only one of ethylene, and, upon binding of one N-2, there is heterolytic splitting of one tBu C-H bond to put the proton on amide N and the carbon on Os, leaving divalent metal in [{PN(H)P-center dot}Os(N-2)(I)]. Two moles of H-2 add, forming [{PN(H)P}OsH(H-2)I], via H-H bond heterolysis. Thermolysis of [(PNP)OsI] gives the product of adding a tBu methyl C-H bond across the Os/N bond, and also net dehydrogenation of this intermediate, forming a carbene complex; the released H-2 forms [(PNP)OsH2I], and the chemistry of [(PNP)Os] hydridohalides is described. Reaction with O-2 occurs with no detectable intermediate, to completely split the O=O bond, and form trans-[(PNP)Os(O)(2)I], a product of four electron redox change. Attempted two electron oxidation by oxygen atom transfer with pyridine N-oxide or Me3NO or N2O surprisingly effect transposition of N from its silyl substituents onto the metal, and replace N by O, forming a nitride complex of a bis(silyl ether, phosphane) chelate whose oxygen fails to bind to Os. The product is thus four-coordinate, tetrahedral [(POP)Os(N)I], with an Os/N triple bond.
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