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), Journal Name: Organometallics; (USA) Vol. 9:1; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
Similar Records
Metal-metal multiple bonds. 20. Structural, kinetic, and theoretical studies of the reactivity of dimolybdenum. mu. -alkylidenes toward small molecules. Structures of M/sub 2/(. mu. -CAr/sub 2/), M/sub 2/(. mu. -CAr/sub 2/'), and M/sub 2/(. mu. -eta/sup 1/,eta/sup 2/-i-PrNC = CAr/sub 2/') (M = Cp(or Cp')Mo(CO)/sub 2/, Ar = p-Tolyl, Ar/sub 2/' = 2,2'-biphenylenyl, and Cp' = C/sub 5/H/sub 4/Me)
Heterometallic analogues of ((. eta. sup 5 -C sub 5 Me sub 5 )M(CO) sub 2 ) sub 2 (M = Fe, Ru, Os). Synthesis and structures of (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 (CO) sub 4 IrRe, (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 (CO) sub 4 IrMn, and (. eta. sup 5 -C sub 5 Me sub 5 )(. eta. sup 5 -C sub 5 H sub 5 )(CO) sub 4 IrRe
Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 )
Journal Article
·
Wed Jun 10 00:00:00 EDT 1987
· J. Am. Chem. Soc.; (United States)
·
OSTI ID:6036753
Heterometallic analogues of ((. eta. sup 5 -C sub 5 Me sub 5 )M(CO) sub 2 ) sub 2 (M = Fe, Ru, Os). Synthesis and structures of (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 (CO) sub 4 IrRe, (. eta. sup 5 -C sub 5 Me sub 5 ) sub 2 (CO) sub 4 IrMn, and (. eta. sup 5 -C sub 5 Me sub 5 )(. eta. sup 5 -C sub 5 H sub 5 )(CO) sub 4 IrRe
Journal Article
·
Mon Oct 01 00:00:00 EDT 1990
· Organometallics; (United States)
·
OSTI ID:5943495
Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 )
Journal Article
·
Tue May 01 00:00:00 EDT 1990
· Organometallics; (USA)
·
OSTI ID:6429153
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200* -- Inorganic
Organic
& Physical Chemistry
ALKYNES
CATALYSTS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
TANTALUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
400200* -- Inorganic
Organic
& Physical Chemistry
ALKYNES
CATALYSTS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
TANTALUM COMPLEXES
TRANSITION ELEMENT COMPLEXES