Sulfur-hydrogen and selenium-hydrogen bond activation by both metal centers in [MM[prime](CO)[sub 3](Ph[sub 2]PCH[sub 2]PPh[sub 2])[sub 2]] (M, M[prime] = Rh, Ir)

Journal Article · Wed Apr 28 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00061a024· OSTI ID:6259691

McDonald, R; Cowie, M ^[1]

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1. Univ. of Alberta, Edmonton (Canada)

The complexes [M[sub 2](CO)[sub 3](dppm)[sub 2]] (M = Rh (1), Ir (2); dppm = Ph[sub 2]PCH[sub 2]PPh[sub 2]) react with H[sub 2]S to produce [M[sub 2](CO)[sub 2]([mu]-S)(dppm)[sub 2]], CO, and H[sub 2]; the reaction is immediate and quantitative for M = Rh, while for M = Ir a number of hydridic intermediates of general formula [Ir[sub 2](H)[sub 2](CO)[sub 2]([mu]-S)(dppm)[sub 2]] are observed, allowing a mechanism for H[sub 2]S addition and H[sub 2] elimination to be proposed. Reaction of H[sub 2]S with 1 leads to several unidentified products, while with 2 hydridic products analogous to those observed in the H[sub 2]S reaction are among those formed. The reactions of [RhIr(CO)[sub 3](dppm)[sub 2]] (3) with H[sub 2]S and H[sub 2]Se yield [RhIr(H)(CO)[sub 2]([mu]-XH)(dppm)[sub 2]] (X = S (7), Se (8)), which are proposed to have structures modeling the species formed by the first S-H bond addition to 1 or 2; these undergo no further rearrangement or elimination of H[sub 2]. Reactions of the thiols or selenols RXH (X = S, R = Et, Ph; X = Se, R = Ph) with 1 or 3 do not yield characterizable products; however with 2, complexes of the form [Ir[sub 2](XR)[sub 2](CO)[sub 2]([mu]-CO)(dppm)[sub 2]] are obtained. One of these, [Ir[sub 2](SPh)[sub 2](CO)[sub 2]([mu]-CO)(dppm)[sub 2]] (17), has been characterized by X-ray crystallography and is shown to have the SPh ligands disposed on one side of the Ir[sub 2]P[sub 4] plane, while the one bridging and two terminal CO ligands are found on the opposite side. Although, in contrast to the reactions of 2 with H[sub 2]S and H[sub 2]Se, net loss of CO does not occur in the formation of the dithiolate and diselenolate products, monitoring the reactions of 2 with RSH through use of variable-temperature multinuclear NMR spectroscopy indicates that dicarbonyl species such as [Ir[sub 2](H)[sub 2](SR)[sub 2](CO)[sub 2](dppm)[sub 2]] are intermediates. 41 refs., 1 fig., 7 tabs.

• OSTI ID: 6259691
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:9; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010402 -- Coal
Lignite
& Peat-- Purification & Upgrading
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL ACTIVATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CRYSTALLOGRAPHY
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
IRIDIUM COMPLEXES
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION INTERMEDIATES
RESONANCE
RHODIUM COMPLEXES
SELENIUM COMPOUNDS
SELENIUM HYDRIDES
SULFIDES
SULFUR COMPOUNDS
THIOLS
TRANSITION ELEMENT COMPLEXES
YIELDS