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Reactions of the electron-rich binuclear hydride complexes [[Pr[sub 2][sup i]P(CH[sub 2])[sub x]PPr[sub 2][sup i]]RH][sub 2] ([mu]-H)[sub 2] (x = 2 or 3) with ZnR[sub 2] and MgR[prime][sub 2]

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00030a027· OSTI ID:6258758
; ;  [1]
  1. Univ. of British Columbia, Vancouver (Canada)
+ Show Author Affiliations
The reaction of dialkylzine reagents (ZnR[sub 2]; R = CH[sub 2]Ph, C[sub 5]H[sub 5], C[sub 3]H[sub 5]) with the binuclear hydride dimers [P[sub 2]Rh][sub 2]([mu]-H)[sub 2] (P[sub 2] = dippe = 1,3-bis(diisoprophylphosphino)propane, dippe = 1,2-bis(diisoprophylphosphino)ethane) yields two products: the first is a mononuclear Rh(I) derivative P[sub 2]RhR and the second is a tetranuclear complex of the general formula [P[sub 2]Rh][sub 2]([mu]-H)[sub 2]([mu]-ZnR)[sub 2]. Two of the tetranuclear species have been studied crystallographically. The molecular structure of [(dippp)Rh][sub 2]([mu]-H)[sub 2]([mu]-ZnCH[sub 2]Ph)[sub 2] (a = 19.608(7) A, b = 12.891(6) A, c = 22.847(6) A, [beta] = 120.02(2)[degrees], Z = 4, fw = 1073.61, [rho](calcd) = 1.426 g cm[sup [minus]3], space group = C2/c) reveals a dirhodium core symmetrically bridged by two hydrides and two ZnCH[sub 2]Ph units. The reaction of dibenzylmagnesium with [(dippp)Rh][sub 2]([mu]-H)[sub 2] is similar in that the Rh(I) species (dippp)Rh([eta][sup 3]-CH[sub 2]Ph) is formed; however, the second product is believed to be the heterobimetallic complex P[sub 2]RhH[sub 2]MgCH[sub 2]Ph that does not dimerize. The Rh-Zn complexes react reversibly with dihydrogen to give binuclear polyhydrides that are in equilibrium with monomeric Rh(III) complexes of the form P[sub 2]RhH[sub 2]ZnR. The Rh-Mg complex reacts reversibly with dihydrogen to give a heterobinuclear tetrahydride. Mechanistic studies are presented that show the formation of the Rh-Zn tetranuclear species involves fragmentation followed by recombination steps. 45 refs., 6 figs., 5 tabs.
OSTI ID:
6258758
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:6; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English

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Related Subjects

08 HYDROGEN
080201 -- Hydrogen-- Chemisorption Storage
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ALKALINE EARTH METAL COMPOUNDS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN STORAGE
INFORMATION
MAGNESIUM COMPOUNDS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHORUS COMPOUNDS
RESONANCE
RHODIUM COMPLEXES
STORAGE
TRANSITION ELEMENT COMPLEXES
ZINC COMPOUNDS