Insertion and alkyne coupling reactions on early-transition-metal centers. Structures of CpTa(ME)(. eta. sup 2 -ArCCAr)(. eta. sup 2 -MeCN sup t Bu), CpMeTaC(Ph)C(Ph)C(Me)N sup t Bu, and CpClMo(CPh) sub 4 (Ar = p-tolyl)
- Univ. of Michigan, Ann Arbor (USA)
CpTaCl{sub 2}({eta}{sup 2}-ArCCAr) (Ar = phenyl, p-tolyl) reacts with MeLi to give a CpTaMe{sub 2}({eta}{sup 2}-ArCCAr) (1) in high yield. Compound 1 reacts with {sup t}BuNC to give the {eta}{sup 2}-acetimidoyl derivatives CpTaMe({eta}{sup 2}-ArCCAr)({eta}{sup 2}-MeCN{sup t}Bu) (4) from the insertion of the isocyanide into one of the Ta-Me bonds. Gentle heating causes a quantitative conversion of 4 into metallacyclopentatriene derivatives, CpMeTaC(Ar)C(Ar)C(Me)N({sup t}Bu) (5), in which the alkyne has coupled to the acetimidoyl ligand with the formation of a new C-C bond. A similar coupling reaction is observed when CpMoCl(ArCCAr){sub 2} is heated in toluene; one of the products of this reaction is the metallacyclopentatriene CpClMo(CAr){sub 4} (7). The metallacyclic ring in 7 features two Mo=C double bonds (d = 1.94 {angstrom}) and the ring is folded (dihedral angle {approx equal}117{degree}). The crystal structures of 4b (Ar = p-tolyl), 5a (Ar = phenyl), and 7a{center dot}CH{sub 2}Cl{sub 2} (Ar = phenyl) have been determined: 4b, a = 10.518 (3) {angstrom}, b = 12.782 (3) {angstrom}, c = 18.816 (6) {angstrom}, {alpha} = {beta} = {gamma} = 90{degree}, V = 2,530 (1) {angstrom}{sup 3}, Z = 4, {rho}{sub c} =1.48 g/mL, space group P2{sub 1}2{sub 1}2{sub 1}, R = 0.027, R{sub w} = 0.026; for 5a, a = 9.540 (3) {angstrom}, b = 10.830 (4) {angstrom}, c = 11.932 (3) {angstrom}, {alpha} = 114.77 (2){degree}, {beta} = 91.47 (2){degree}, {gamma} = 91.68 (3){degree}, V = 1117.8 (6) {angstrom}{sup 3}, Z = 2, {rho}{sub c} = 1.59 g/mL, space group P{bar 1}, R = 0.045, R{sub w} = 0.044; 7a{center dot}CH{sub 2}Cl{sub 2} a = 10.039 (4) {angstrom}, b = 11.760 (3) {angstrom}, c = 12.674 (8) {angstrom}, {alpha} = 92.21 (4){degree}, {beta} = 87.35 (4){degree}, {gamma} = 104.05 (3){degree}, V = 1,449 (1) {angstrom}{sup 3}, Z = 2, {rho}{sub c} = 1.46 g/mL, space group P{bar 1}, R = 0.038, R{sub w} = 0.038.
- OSTI ID:
- 6654792
- Journal Information:
- Organometallics; (USA), Vol. 9:1; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
Similar Records
Reactions of transition-metal. sigma. -acetylide complexes. 14. Cyclobutenyl, butadienyl, and allyl complexes of ruthenium derived from 1,1-dicyano-2,2-bis(trifluoromethyl)ethene. X-ray structures of Ru(C=CPhC(CF sub 3 ) sub 2 C(CN) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ), Ru(C(=C(CN) sub 2 )CX=C(CF sub 3 ) sub 2 )(CO)(PPh sub 3 )(. eta. -C sub 5 H sub 5 ) (X = Me, Ph), and Ru(. eta. sup 3 -C(CF sub 3 ) sub 2 CPhC=C(CN) sub 2 )(PPh sub 3 )(. eta. -C sub 5 H sub 5 )
Alkoxy and aryloxy derivatives of (pentamethylcyclopentadienyl)ruthenium. X-ray crystal structures of ((. eta. sup 5 -C sub 5 Me sub 5 )Ru(. mu. -OMe)) sub 2 , ((. eta. sup 5 -C sub 5 Me sub 5 )(CO)Ru(. mu. -OEt)) sub 2 , and (. eta. sup 5 -C sub 5 Me sub 5 )Ru(. eta. sup 5 -2,6- sup t Bu sub 2 C sub 6 H sub 3 O) and molecular orbital analysis of ((. eta. sup 5 -C sub 5 H sub 5 )Ru(. mu. -OMe)) sub 2
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
TANTALUM COMPLEXES
CRYSTAL STRUCTURE
ALKYNES
CATALYSTS
DATA ANALYSIS
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
TRANSITION ELEMENT COMPLEXES
COMPLEXES
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
400200* - Inorganic
Organic
& Physical Chemistry