[([superscript t]Bu[subscript 2]PCH[subscript 2]SiMe[subscript 2])[subscript 2]N]Rh[superscript I]? Rapidly Reversible H-C(sp[superscript 3]) and H−C(sp[superscript 2]) Bond Cleavage by Rhodium(I)

Journal Article · Fri Oct 03 00:00:00 EDT 2008 · Organometallics

DOI:https://doi.org/10.1021/om701165n· OSTI ID:1007634

Verat, Alexander Y; Pink, Maren; Fan, Hongjun; Tomaszewski, John; Caulton, Kenneth G ^[1]

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1. Indiana

The product of the reaction of (tBu{sub 2}PCH{sub 2}SiMe{sub 2}){sub 2}N{sup -} (MgCl{sup +} salt) with [RhCl(cyclooctene){sub 2}]{sub 2} is a Rh{sup III} complex where one {sup t}Bu methyl C-H bond has oxidatively added to Rh: (PNP*)RhH. This is in rapid exchange among all 9 x 4 C-H bonds of the four {sup t}Bu groups. (PNP*)RhH undergoes oxidative addition equilibrium with the C-H bonds of benzene at {approx}10{sup 3} s{sup -1} at 25 C and oxidatively adds the ring C-H of other arenes. (PNP*)RhH forms {eta}{sup 2}-olefin complexes with several olefins and dehydrogenates allylic C-H bonds to form (PNP)Rh(H){sub 2}.

• Research Organization: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL (US)
• Sponsoring Organization: USDOE
• OSTI ID: 1007634
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: (2) ; 2007 Vol. 27; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CLEAVAGE
ORGANOMETALLIC COMPOUNDS
OXIDATION
RHODIUM COMPOUNDS
SILICON COMPLEXES