Nickel(0) dimer/monomer system with facile and reversible carbon monoxide uptake: Ni/sub 2/(CO)/sub x/(dppm)/sub 2/ (x = 3, 4) and Ni(CO)/sub 3/(eta/sup 1/-dppm)

Journal Article · Wed Mar 30 04:00:00 EST 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00215a018· OSTI ID:7160209

Osborn, J A; Stanley, G G; Bird, P H

Ni(CO)/sub 2/(HC(PPh/sub 2/)/sub 3/) decomposes slowly at room temperature to produce the bis(diphenylphosphino)methane (dppm) bridged nickel(0) dimer Ni/sub 2/(CO)/sub 3/(dppm)/sub 2/ (4). Complex 4 crystallizes in the orthorhombic space group Pbcn with a = 14.015 (2) A, b = 18.784 (5) A, c = 22.743 (8) A, V = 5987 (4) A/sup 3/, and Z = 4. A total of 3913 reflections were collected using Mo K..cap alpha.. radiation, and the structure was solved and refined by using 1237 independent reflections with F/sub o//sup 2/ > 3 sigma(F/sub o/)/sup 2/, leading to a final R/sub 1/ = 0.062. Ignoring the Ni-Ni bond, the structure of 4 shows approximate tetrahedral geometry about the two nickel atoms with an unusual cis arrangement of the two bridging dppm ligands, one bridging carbonyl ligand, and two terminal carbonyl ligands. The molecule sits on a 2-fold axis passing through the bridging carbonyl group, and there are three solvent molecules of benzene per nickel dimer in the unit cell. The Ni-Ni bond distance of 2.603 (4) A is in the proper range for the expected single bond. 4 readily reacts with 1 equiv of carbon monoxide under ambient conditions to form the 18-electron binuclear complex with terminal CO ligands, Ni/sub 2/(CO)/sub 4/(dppm)/sub 2/ (5), which has been characterized spectroscopically. Although 5 is a saturated 18-electron species, it also readily reacts with CO to fragment, producing Ni(CO)/sub 3/(eta/sup 1/-dppm) (6) in which the dppm ligand is only bound by one phosphorus atom. Spectroscopic data on 6 supporting the Ni(CO)/sub 3/(eta/sup 1/-dppm) formulation are presented. The CO-based equilibrium 4 reversible 5 reversible 6 is fully reversible in solution.

• Research Organization: Universite Louis Pasteur, Strasbourg (France)
• OSTI ID: 7160209
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:7; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIMERS
EXPERIMENTAL DATA
INFORMATION
ISOTOPES
LIGANDS
LIGHT NUCLEI
MAGNETIC RESONANCE
MONOMERS
NICKEL COMPLEXES
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
OXIDES
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS 31
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
RESONANCE
SPACE GROUPS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES