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1.
Dalton Trans ; (18): 2943-51, 2004 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-15349171

RESUMO

Group 5 metal complexes [M(eta5-C5H5)[eta5-C5H4SiMe2(CH2-eta]2-CH=CH2)]X] (M = Nb, X = Me, CH2Ph, CH2SiMe3; M = Ta, X = Me, CH2Ph) and [Ta(eta5-C5Me5)[eta5-C5H4SiMe2(CH2-eta2-CH=CH2)]X] (X = Cl, Me, CH2Ph, CH2SiMe3) containing a chelating alkene ligand tethered to a cyclopentadienyl ring have been synthesized in high yields by reduction with Na/Hg (X = Cl) and alkylation with reductive elimination (X = alkyl) of the corresponding metal(iv) dichlorides [M(eta5-Cp)[eta5-C5H4SiMe2(CH2CH=CH2)]Cl2] (Cp = C5H5, M = Nb, Ta, Cp = C5Me5, M = Ta). These chloro- and alkyl-alkene coordinated complexes react with CO and isocyanides [CNtBu, CN(2,6-Me2C6H3)] to give the ligand-substituted metal(III) compounds [M(eta5-Cp)[eta5-C5H4SiMe2(CH2CH=CH2)]XL] (X = Cl, Me, CH2Ph, CH2SiMe3). Reaction of the chloro-alkene tantalum complex with LiNHtBu results in formation of the imido hydride derivative [Ta(eta5-C5Me5)[eta5-C5H4SiMe2(CH2CH=CH2)]H(NtBu)]. NMR studies for all of the new compounds and DFT calculations for the alkene-coordinated metal complexes are compared with those known for related group 4 metal cations.

2.
Chemistry ; 9(10): 2337-46, 2003 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-12772309

RESUMO

Treatment of [[Ti(eta(5)-C(5)Me(5))(micro-NH)](3)(micro(3)-N)] (1) with the imido complexes [Ti(NAr)Cl(2)(py)(3)] (Ar=2,4,6-C(6)H(2)Me(3)) and [Ti(NtBu)Cl(2)(py)(3)] in toluene affords the single azatitanocubanes [[Cl(2)(ArN)Ti]( micro(3)-NH)(3)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]].(C(7)H(8)) (2.C(7)H(8)) and [[Cl(2)Ti](micro(3)-N)(2)(micro(3)-NH)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]] (3), respectively. Similar reactions of complex 1 with the niobium and tantalum imido derivatives [[M(NtBu)(NHtBu)Cl(2)(NH(2)tBu)](2)] (M=Nb, Ta) in toluene give the single azaheterometallocubanes [[Cl(2)(tBuN)M](micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]] (M=Nb (4), Ta (5)), both complexes react with 2,4,6-trimethylaniline to yield the analogous species [[Cl(2)(ArN)M](micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]].(C(7)H(8)) (Ar=2,4,6-C(6)H(2)Me(3), M=Nb (6.C(7)H(8)), Ta (7.C(7)H(8))). Also the azaheterodicubanes [M[micro(3)-N)(2)(micro(3)-NH)](2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)](2)].2C(7)H(8) [M=Ti (8.2C(7)H(8)), Zr (9.2C(7)H(8))], and [M[(micro(3)-N)(5)(micro(3)-NH)][Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)](2)].2 C(7)H(8) (Nb (10.2C(7)H(8)), Ta (11.2C(7)H(8))) were prepared from 1 and the homoleptic dimethylamido complex [M(NMe(2))(x)] (x=4, M=Ti, Zr; x=5, M=Nb, Ta) in toluene at 150 degrees C. X-ray crystal structure determinations were performed for 6 and 10, which revealed a cube- and double-cube-type core, respectively. For complexes 2 and 4-7 we observed and studied by DNMR a rotation or trigonal-twist of the organometallic ligands [[Ti(eta(5)-C(5)Me(5))(micro-NH)](3)(micro(3)-N)] (1) and [(micro(3)-N)(micro(3)-NH)(2)[Ti(3)(eta(5)-C(5)Me(5))(3)(micro(3)-N)]](1-). Density functional theory calculations were carried out on model complexes of 2, 3, and 8 to establish and understand their structures.

3.
Chemistry ; 8(4): 805-11, 2002 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-11857695

RESUMO

The photochemical treatment of mu(3)-alkylidyne complexes [[TiCp*(mu-O)](3)(mu(3)-CR)] (R=H (1), Me (2), Cp*=eta(5)-C(5)Me(5)) with the amines (2,6-Me(2)C(6)H(3))NH(2), Et(2)NH, and Ph(2)NH and the imine Ph(2)C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti(3)Cp*O(3)], and the formation of new oxoderivatives [[TiCp*(3)(mu-CHR)(R'NR")] (R"=2,6-Me(2)C(6)H(3), R'=H, R=H (3), Me (4); R'=R"=Et, R=H (5), Me (6); R'=R"=Ph, R=H (7), Me (8)) and [[TiCp*(mu-O)](3)(mu-CHR)(N=CPh(2))] (R=H (9), R=Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the mu-methylene [[TiCp*(mu-O)](3)(mu-CH(2))(HNtBu)] (11) complex and finally, the alkyl derivative [[TiCp*(mu-O)](3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes 1 or 2 in the presence of diamines o-C(6)H(4)(NH(2))(2) and H(2)NCH(2)CH(2)NH(2) (en) affords [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(6)H(4)NH)] (13) and [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(2)H(4)NH)] (14) by either methane or ethane elimination, respectively. In the reaction of 1 with en, an intermediate complex [[TiCp*(mu-O)](3)(mu-CH(2))(NHCH(2)CH(2)NH(2))] (15) is detected by (1)H NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R'(2)NH or the imine Ph(2)C=NH; however, heating of solutions of 3 or 4 in [D(6)]benzene or a equimolecular mixture of both at 170 degrees C produces methane, ethane, or both, and the complex [[TiCp*(mu-O)](3)[mu(3)-eta(2)-NC(6)H(3)(Me)CH(2)]] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis.

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