Group 13 and 14 Alkyl Derivatives of the Imido−Nitrido Metalloligand [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]

García-Castro, María; Martı́n, Avelino; Mena, and Miguel; Yélamos, Carlos

doi:10.1021/om060895+

Cited by 18 publications

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References 56 publications

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“…Las estructuras cristalinas de los complejos 5, 11, 13, 14 y [AlCl{NA C H T U N G T R E N N U N G (SiMe 3 ) 2 } 2 ] se han determinado mediante difracción de rayos-X de monocristal. 3 [19] 8 ]tetrahydrofuran), and their lack of volatility precludes their characterization by mass spectrometry (EI, 70 eV). Therefore, the compounds were only characterized by IR spectroscopy and C, H, N microanalysis.…”

Section: Resultsmentioning

confidence: 99%

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Molecular Nitrides with Titanium and Group 13–15 Elements

García-Castro¹,

Martı́n²,

Mena³

et al. 2009

Chemistry A European J

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Several heterometallic nitrido complexes were prepared by reaction of the imido-nitrido titanium complex [{Ti(eta(5)-C(5)Me(5))(mu-NH)}(3)(mu(3)-N)] (1) with amido derivatives of Group 13-15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe(3))(2)}(3)] derivatives of aluminum, gallium, or indium in toluene at 150-190 degrees C affords the single-cube amidoaluminum complex [{(Me(3)Si)(2)N}Al{(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] (2) or the corner-shared double-cube compounds [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] [M = Ga (3), In (4)]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH(2)SiMe(3))(3)] (M = Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe(2))(3)}(2)] at 110 degrees C leads to [{Ga(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] (5), in which two [GaTi(3)N(4)] cube-type moieties are linked through a gallium-gallium bond. Complex 1 reacts with one equivalent of germanium, tin, or lead bis(trimethylsilyl)amido derivatives [M{N(SiMe(3))(2)}(2)] in toluene at room temperature to give cube-type complexes [M{(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] [M = Ge (6), Sn (7), Pb (8)]. Monitoring the reaction of 1 with [Sn{N(SiMe(3))(2)}(2)] and [Sn(C(5)H(5))(2)] by NMR spectroscopy allows the identification of intermediates [RSn{(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] [R = N(SiMe(3))(2) (9), C(5)H(5) (10)] in the formation of 7. Addition of one equivalent of the metalloligand 1 to a solution of lead derivative 8 or the treatment of 1 with a half equivalent of [Pb{N(SiMe(3))(2)}(2)] afford the corner-shared double-cube compound [Pb(mu(3)-N)(2)(mu(3)-NH)(4){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] (11). Analogous antimony and bismuth derivatives [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] [M = Sb (12), Bi (13)] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe(2))(3)]. Treatment of 1 with [AlCl(2){N(SiMe(3))(2)}(OEt(2))] affords the precipitation of the singular aluminum-titanium square-pyramidal aggregate [{{(Me(3)Si)(2)N}Cl(3)Al(2)}(mu(3)-N)(mu(3)-NH)(2){Ti(3)(eta(5)-C(5)Me(5))(3)(mu-Cl)(mu(3)-N)}] (14). The X-ray crystal structures of 5, 11, 13, 14, and [AlCl{N(SiMe(3))(2)}(2)] were determined.

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Section: Resultsmentioning

confidence: 99%

“…[17,18] In particular, we recently reported the reactivity of 1 toward alkyl derivatives of Group 13 and 14 elements. [19] In a fashion similar to that of organic macrocyclic amines, [20] complex 1 acts as chelate to a single Group 13 center to form adducts [R 3 …”

Section: H T U N G T R E N N U N G {(M 3 -N) 2 a C H T U N G T R E N mentioning

confidence: 99%

Molecular Nitrides with Titanium and Group 13–15 Elements

García-Castro¹,

Martı́n²,

Mena³

et al. 2009

Chemistry A European J

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“…Biochem. 69, 37(2005 Di(thiophenyl)ethene ligands are of interest as prototypes for 'molecular switches' in future molecular electronic applications [1,2]. In this contribution we describe the synthesis of metal complexes of a di(thiophenyl)ethene ligand in the 'open' form, photolysis of which reversibly gives the 'closed' form (see Figure).…”

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confidence: 99%

“…The highlights from the published work, presented in this poster, show the systematic contribution of the structural investigation, not only as the ultimate means towards the identifi cation of expected and unexpected products, but also as an effective tool for underpinning reaction pathways and intermediates. The conductivity by proton in bulk such as a copper rubeanate complex has been studied [1]. Such complexes which consist of thin layers can be useful for a part of a fuel cell.…”

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Structural study of an iron oxalate and a copper rubeanate layer on an ultra-smooth sapphirec-face

Haruki¹,

Sakata²,

Yamada³

et al. 2008

Acta Cryst Sect A

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Lewis Base Behavior of Bridging Nitrido Ligands of Titanium Polynuclear Complexes

Carbó

Martínez-Espada

Mena

et al. 2009

Chemistry A European J

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The Lewis base behavior of mu3-nitrido ligands of the polynuclear titanium complexes [{Ti(eta5-C5Me5)(mu-NH)}3(mu3-N)] (1) and [{Ti(eta5-C5Me5)}4(mu3-N)4] (2) to MX Lewis acids has been observed for the first time. Complex 1 entraps one equivalent of copper(I) halide or copper(I) trifluoromethanesulfonate through the basal NH imido groups to give cube-type adducts [XCu{(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)}] (X=Cl (3), Br (4), I (5), OSO2CF3 (6)). However, the treatment of 1 with an excess (> or = 2 equiv) of copper reagents afforded complexes [XCu{(mu3-NH)3Ti3(eta5-C5Me5)3(mu4-N)(CuX)}] (X=Cl (7), Br (8), I (9), OSO2CF3 (10)) by incorporation of an additional CuX fragment at the mu3-N nitrido apical group. Similarly, the tetranuclear cube-type nitrido derivative 2 is capable of incorporating one, two, or up to three CuX units at the mu3-N ligands to give complexes [{Ti(eta5-C5Me5)}4(mu3-N)(4-n){(mu4-N)CuX}n] (X=Br (11), n=1; X=Cl (12), n=2; X=OSO2CF3 (13), n=3). Compound 2 also reacts with silver(I) trifluoromethanesulfonate (> or = 1 equiv) to give the adduct [{Ti(eta5-C5Me5)}4(mu3-N)3{(mu4-N)AgOSO2CF3}] (14). X-ray crystal structure determinations have been performed for complexes 8-13. Density functional theory calculations have been carried out to understand the nature and strength of the interactions of [{Ti(eta5-C5H5)(mu-NH)}3(mu3-N)] (1') and [{Ti(eta5-C5H5)}4(mu3-N)4] (2') model complexes with copper and silver MX fragments. Although coordination through the three basal NH imido groups is thermodynamically preferred in the case of 1', in both complexes the mu3-nitrido groups act as two-electron donor Lewis bases to the appropriate Lewis acids.

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Group 13 and 14 Alkyl Derivatives of the Imido−Nitrido Metalloligand [{Ti(η⁵-C₅Me₅)(μ-NH)}₃(μ₃-N)]

Cited by 18 publications

References 56 publications

Molecular Nitrides with Titanium and Group 13–15 Elements

Molecular Nitrides with Titanium and Group 13–15 Elements

Structural study of an iron oxalate and a copper rubeanate layer on an ultra-smooth sapphirec-face

Lewis Base Behavior of Bridging Nitrido Ligands of Titanium Polynuclear Complexes

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