Photoinduced carbonylation of the carbyne ligand in (eta-C/sub 5/H/sub 5/)(CO)/sub 2/W=CTol

Journal Article · Mon Feb 01 04:00:00 EST 1988 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00092a009· OSTI ID:7004346

Sheridan, J b; Pourreau, D B; Geoffroy, G L

UV irradiation of solutions of Cp(CO)/sub 2/W=CTol (1) (Tol = rho-C/sub 6/H/sub 4/CH/sub 3/; Cp = eta-C/sub 5/H/sub 5/) in the presence of CO induces carbonylation of the carbyne ligand and formation of the binuclear complex (Cp-(CO)/sub 2/W)/sub 2/(eta-TolCC/O/CTol) (2). Complex 2 has been crystallographically characterized: triclinic, P anti 1, a = 8.773 (2) A, b = 12.042 (3) A, c = 14.866 (5) A, ..cap alpha.. = 91.81 (2)/sup 0/, ..beta.. = 94.12 (2)/sup 0/, ..gamma.. = 110.32 (2)/sup 0/, R/sub F/ = 4.63%, R/sub wF/ = 5.62% for 3075 reflections with F/sub o/ greater than or equal to 3 sigma(F/sub o/). The bridging ligand of 2 consists of two carbyne units linked by a CO with the latter not bonded to either metal. Irradiation of 1 in the presence of PPh/sub 3/ leads to rapid formation of the known ketenyl complex Cp(CO)/sub 2/(PPh/sub 3/)W(eta/sup 2/-TolCCO) (5). Complex 5 reacts further with CO to form the eta/sup 1/-ketenyl species Cp(CO)/sub 2/(PPh/sub 3/)W(eta/sup 1/-TolCCO). Photolysis of 1 in the presence of dppe (dppe = 1,2 bis(diphenylphosphino)ethane) yields the eta/sup 1/-ketenyl species Cp(CO)(dppe)W(eta/sup 1/-TolCCO), which readily loses dppe to give the novel binuclear eta/sup 2/-ketenyl species Cp(CO)(dppe)W(eta/sup 1/-TolCCO), which readily loses dppe to five the novel binuclear eta/sup 2/-ketenyl derivative (Cp(CO)W(eta/sup 2/-TolCCO))/sub 2/(..mu..-dppe).

• Research Organization: Pennsylvania State Univ., University Park (USA)
• OSTI ID: 7004346
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:2; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
BOND ANGLE
BOND LENGTHS
CARBONYLATION
CARBONYLS
CARBYNES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIMENSIONS
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
INFORMATION
KETENES
LENGTH
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADICALS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES