Cadmium and mercury complexes containing trinuclear titanium imido-nitrido metalloligands

Several heterometallic nitrido complexes have been prepared from the reaction of the trinuclear imido-nitrido titanium complex [{Ti(5-C5Me5)(mu-NH)}3(mu 3-N)] (1) with cadmium and mercury derivatives. Treatment of 1 with cadmium dichloride or cadmium diiodide in toluene afforded the adducts [X2Cd{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] [X = Cl (2), I (3)]. Complex 2 reacted with lithium reagents [LiR] in toluene to give the cube-type derivatives [RCd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(mu 3-N)}] [R = CH2SiMe3 (4), C=CSiMe3 (5), C5H4(SiMe3) (6), N(SiMe3)2 (7)]. The amido complex 7 reacted with 1 equiv. of 1 to give the corner-shared double-cube complex [Cd{(mu 3-N)(mu 3-NH)2Ti3(5-C5Me5)3(rho 3-N)}2] (8) by means of bis(trimethylsilyl)amine elimination. Treatment of 1 with mercury(II) iodide in toluene gave the adduct [I2Hg{(mu 3-NH)3Ti3(5-C5Me5)3(mu 3-N)}] (9), which reacted with [K{N(SiMe3)2}] to afford [Hg{(mu 3-N)2Ti3(5-C5Me5)3(mu-NH)(mu 3-N)}]2 (10) through the amido mercury intermediate [{(Me3Si)2N}Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (11). Compound 11 and the analogous alkyl derivative [(Me3SiCH2)Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}] (12) were characterised by NMR spectroscopy upon the treatment of 1 with [Hg{N(SiMe3)2}R] [R = N(SiMe3)2, CH2SiMe3]. Complex [Hg{(mu 3-N)Ti3(5-C5Me5)3(mu-NH)2(mu 3-N)}2] (13), with one bridging mercury atom between two titanium trinuclear systems, was obtained upon treatment of HgI2 with the potassium derivative [K(mu 4-N)(mu 3-NH)2{Ti3(5-C5Me5)3(mu 3-N)}]2. Complexes 3, 5 and 8 were characterised by single-crystal X-ray diffraction analysis.Ministerio de Educación y Ciencia de Españ

Molecular Nitrides with Titanium and Group 13-15 Elements

MINISTERIO DE EDUCACIÓN Y CIENCIA, COMUNIDAD DE MADRID, UNIVERSIDAD DE ALCAL

Cube-Type Nitrido Complexes Containing Titanium and Alkali/Alkaline-Earth Metals

(M = Ca, Sr) have been determined. The properties and solid-state structures of the azaheterometallocubane complexes bearing alkali and alkaline-earth metals are discussed.Ministerio de Ciencia y Tecnología de España, Comunidad de Madrid, Universidad de Alcal

Amido-bridged double cube nitrido complexes containing titanium and magnesium/calcium

Treatment of the single cube nitrido complexes [(thf)(x){(Me3Si)(2)N} M{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Mg, x = 0; Ca, x = 1) with one equivalent of anilines NH2Ar in toluene affords the arylamido complexes [(ArHN) M{(mu(3)-N)(mu(3)- NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}](n) [M = Mg ( 3), n = 1, Ar = 4-MeC6H4; Ca (4), n = 2, Ar = 2,4,6-Me3C6H2]. The magnesium complex 3 has a single-cube structure whereas the X-ray crystal structure of the analogous calcium derivative 4 shows two cube-type azaheterometallocubane moieties "Ca{(mu(3)-N)(mu(3)- NH)(2)Ti-3(eta(C5Me5)-C-5) (3)(mu(3)-N)}" held together by two mu-2,4,6-trimethylanilido ligands. Complexes 3 and 4 react with chloroform-d(1) at room temperature to give the metal halide adducts [Cl2M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)- N)}] (M = Mg, Ca). A solution of 3 in n-hexane gave complex [{Mg-2(mu(3)-N)(mu(3)-NH)(5)[ Ti-3(eta(5)- C5Me5)(3)(mu(3)- N)](2)}(mu-NHAr)(3)] which shows three mu-4-methylanilido ligands bridging two [MgTi3N4] cube type cores according to an X-ray crystal structure determination.Ministerio de Ciencia y Tecnología, Comunidad de Madri

Copper(I) and Silver(I) Complexes Supported by the Tridentate [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] Metalloligand

(2) (M = Cu (18), Ag (19)). The X-ray crystal structures of 4, 5, 10, 14, 15, and 18 have been determined.Ministerio de Educación y Ciencia de Españ

Cube-Type Nitrido Complexes Containing Titanium and Zinc/Copper

Several azaheterometallocubane complexes containing [MTi3N4] cores have been prepared by the reaction of [{Ti(eta(C5Me5)-C-5)( mu-NH)}(3)(mu(3)-N)] (1) with zinc(II) and copper(I) derivatives. The treatment of 1 with zinc dichloride in toluene at room temperature produces the adduct [Cl2Zn {(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (2). Attempts to crystallize 2 in dichloromethane gave yellow crystals of the ammonia adduct [(H3N) Cl2Zn {(mu(3)-NH) Ti-3(eta(5)-C5Me5)(3)(mu-NH)(2)(mu(3)- N)}] ( 3). The analogous reaction of 1 with alkyl, ( trimethylsilyl) cyclopentadienyl, or amido zinc complexes [ ZnR2] leads to the cube-type derivatives [RZn {(A(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (R) CH2SiMe3 (5), CH2Ph (6), Me ( 7), C5H4SiMe3 (8), N(SiMe3)(2) (9)) via RH elimination. The amido complex 9 decomposes in the presence of ambient light to generate the alkyl derivative [{Me3Si(H) N(Me) 2SiCH2} Zn {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (10). The chloride complex 2 reacts with lithium cyclopentadienyl or lithium indenyl reagents to give the cyclopentadienyl or indenyl zinc derivatives [RZn {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (R) C5H5 (11), C9H7 (12)). Treatment of 1 with copper(1) halides in toluene at room temperature leads to the adducts [XCu {(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] ( X) Cl ( 13), I (14)). Complex 13 reacts with lithium bis( trimethylsilyl) amido in toluene to give the precipitation of [{Cu(mu(4)-N)(mu(3)- NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)- N)}(2)] (15). Complex 15 is prepared in a higher yield through the reaction of 1 with [{CuN(SiMe3)(2)}(4)] in toluene at 150 degrees C. The addition of triphenylphosphane to 15 in toluene produces the single-cube compound [( Ph3P) Cu {(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (16). The X-ray crystal structures of 3, 8, 9, and 15 have been determined.Ministerio de Ciencia y Tecnología de España, Comunidad de Madrid, Universidad de Alcal

Molecular Nitrides with Titanium and Rare-Earth Metals

A series of titanium-group 3/lanthanide metal complexes have been prepared by reaction of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] (1) with halide, triflate, or amido derivatives of the rare-earth metals. Treatment of 1 with metal halide complexes [MCl3(thf)(n)] or metal trifluoromethanesulfonate derivatives [M(O3SCF3)(3)] at room temperature affords the cube-type adducts [X3M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (X = Cl, M = Sc (2), Y (3), La (4), Sm (5), Er (6), Lu (7); X = OTf, M = Y (8), Sm (9), Er (10)). Treatment of yttrium (3) and lanthanum (4) halide complexes with 3 equiv of lithium 2,6-dimethylphenoxido [LiOAr] produces the aryloxido complexes [(ArO)(3)M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Y (11), La (12)). Complex 1 reacts with 0.5 equiv of rare-earth bis(trimethylsilyl)amido derivatives [M{N(SiMe3)(2)}(3)] in toluene at 85-180 degrees C to afford the corner-shared double-cube nitrido compounds [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = Sc (13), Y (14), La (15), Sm (16), Eu (17), Er (18), Lu (19)) via NH(SiMe3)(2) elimination. A single-cube intermediate [{(Me3Si)(2)N}Sc{(mu(3)-N)(2)(mu(3)-NH)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (20) was obtained by the treatment of 1 with 1 equiv of the scandium bis(trimethylsilyl)amido derivative [Sc{N(SiMe3)(2)}(3)]. The X-ray crystal structures of 2, 7, 11, 14, 15, and 19 have been determined. The thermal decomposition in the solid state of double-cube nitrido complexes 14, 15, and 18 has been investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements, as well as by pyrolysis experiments at 1100 degrees C under different atmospheres (Ar, H-2/N-2, NH3) for the yttrium complex 14.Ministerio de Educación y Ciencia de España, Comunidad de Madrid, Universidad de Alcal

Mercury or Silver Atoms Bridging Trinuclear Titanium Imido-Nitrido Systems

The imido - nitrido complex [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] entraps mercury(II) or silver(I) halides MXn to give cube-type adducts [XnM{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] which react with alkali metal bis(trimethylsilyl) amide reagents to afford [M-2{(mu(3)-N)(n)(mu(3)-NH)(2-n)Ti-3(eta(5)-C5Me5)(3)(mu-NH)(mu(3)-N)}(2)] (M = Hg, n = 2; M = Ag, n = 1) where two [Ti3N4] cores are linked by two mercury or silver atoms in a linear geometry.Ministerio de Educación y Ciencia de España, Comunidad de Madrid, Universidad de Alcal

Pentamethylcyclopentadienyl halo- and alkyl-alkoxo tantalum(V) complexes. Crystal structure of TaCp*(CH2SiMe3) 2{η2-O(2-CH2-6-MeC6H3)}

Reaction of TaCp" C! 4 with MOR (M - Li, Na) in different molar ratios gives halo alkoxides TaCp" CI,(OR)4_,, (n - 3: R -tBu 1; $iPh 3 2; 2,6-Me2C6H 3 3; n -- 2: R -~Bu 4; SiPh 3 5; 2,6-Me2C6H3 6; a - !: R - SiMe 3 7) in good yields. The alkylidene complex TaCp'(CH2SiMe,02(CHSiMe ~) is hydrolyzed in the presence of traces of water to give the oxo dialkyl derivative [TaCp'(CH2SiM¢3)~O],, 8, and reacts with I equivalent of 2,6-MezC6H~NC affording a new 'q2-iminoacyi compound TaCp" (CH 2$iMe3XCHSiMe3){~ 2"C(CH 2SiMe3 ) = N(2,6"MeaC6 H 3)} 9. Reactions of TaCp "(CH 2SiMe3)a(CHSiMe3 ) with I equivalent of C6HsOH and 4-MeC6H3(OH) 2 result in the formation of the alkyl phenoxo TaCp'(CH2SiMe3)3(OC6Hs) 10 and 4-methyl pyrocatecholate TaCp'(CH2SiMe~)2(O2C6H3Me) 11, whereas the related re,",,:don with 2,6-Me2C6H 3OH leads to the cyclic alkyi-aikoxo compound TaCp (CH2SiMej)2(~2-O(2-CH2-6-MeC6H3)) 12. All the complexes were characterized by IR and NMR (tH and 13C) spectroscopy. The crystal and molecular structure of 12 has been determine~i. C~ystals of 12 are triclinic, space group P'[ with Z - 2 in a unit cell of dimensions a- 9.151(5) ~, b- 11.835(5) ~,, c- 14.045(4) A, a- 89.35(3) °, /3- 72.34(3) 0 and 'y-88.51(4) °, V- 1449(I) ~s. Final values of R -0.025 and Rw -0.0655 were obtained from 554'7 reflections measured (50'70, > 2o'(i))

Alkyl and alkylidene imido cyclopentadienyl tungsten complexes

This paper reports the alkylation of the cyclopentadienyl imido tungsten complexes [WCp′(NtBu)Cl3] (Cp′=η5-C5H5, η5-C5Me5) with β-hydrogen containing alkyl groups to render halo alkyl and trialkyl complexes [WCp′(NtBu)Cl3−nRn] (R=Et, n-Pr). Thermal decomposition of the trialkyl compounds gives the alkylidene derivatives [WCp′(NtBu)(CHR)(CH2R)] (R=Me, Et) by α-hydrogen elimination. All of the compounds were characterized by NMR spectroscopy and the molecular structure of [W(η5-C5Me5)(NtBu)Et3] was determined by X-ray diffraction methods.The authors acknowledge DGICYT (project PB97-0677) for financial support