Intramolecular versus intermolecular bonding in amidoantimony dimers; syntheses and structures of {Sb(NMe2)[µ-N(mpy)]}2(mpy = 4-methylpyridin-2-yl) and [Sb(NMe2){µ-N[C6H2(OMe)3-3,4,5]}]2

Edwards, Andrew J.; Paver, Michael A.; Rennie, Moira-Ann; Raithby, Paul R.; Russell, Christopher A.; Wright, Dominic S.

doi:10.1039/dt9940002963

Cited by 18 publications

(15 citation statements)

References 9 publications

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“…3, eqn ( 4)) containing a central E 2 N 2 core with each metal centre bonding to a pendant basic NMe 2 arm in which the NMe 2 groups are arranged trans to each other. 57 Similar structures have been observed for example in…”

Section: Perspective Dalton Transactionssupporting

confidence: 86%

Applications and reactivity trends of homoleptic p-block metal amido reagents

Melen¹

2013

Dalton Trans.

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This review aims to develop an understanding of reactivity trends of p-block metal bases M(NR2)n (M = Sn: n = 2; M = Al, Ga, As, Sb: n = 3) towards organic substrates EHy containing one or more E-H bonds (E = B, N, P, S). These compounds not only act as good bases for the deprotonation of E-H bonds but recent advances in p-block amido chemistry have shown that, in addition, they can effect the dehydrogenic homo-coupling of primary phosphines and amines to give E-E bonded products. They have also been found to be active in stoichiometric and catalytic dehydrocoupling of amine-boranes, which has direct applications in hydrogen storage devices, revealing that these p-block catalysts offer potential alternatives to the extensive range of expensive and often highly toxic heavy metal catalysts. This perspective analyses three distinct reactivity patterns of p-block metal bases; deprotonation, stoichiometric dehydrocoupling and catalytic dehydrocoupling and attempts to rationalise reactivity in relation to the redox stability of the p-block metal.

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Section: Perspective Dalton Transactionssupporting

confidence: 86%

Applications and reactivity trends of homoleptic p-block metal amido reagents

Melen¹

2013

Dalton Trans.

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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%

“…are obtained depending on the steric demand of the ligands at the metal and nitrogen atoms, the temperature, and the solvent used. [6][7][8] Nitrido complexes of the early transition metals (Groups 4 and 5) also constitute a class of molecular compounds with singular polynuclear structures.…”

Section: Introductionmentioning

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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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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“…We thank the Natural Sciences and Engineering Research Council of Canada, the Killam Foundation, the Canada Research Chairs Program, and the Sumner Foundation for funding. (5), 436 (9), 494 (14), 543 (11), 670 (13), 770(2), 769(3), 928 (11), 1027 (15), 1098 (12), 1139 (19), 1154 (20), 1211 (6), 1262 (7), 1577 (10), 1598 (8), 3295 (17), 3357 (16), 3374 (18); NMR: 1 H (CDCl 3 ): 2.18 (s), 3.86 (s), 6.69 (t), 6.94 (d); Crystal Data: C 24.5 H 34 Cl 7 N 3 Sb 2 , M 5 862.20 g mol 21 , triclinic, P-1, a 5 9.9556( 7 Isolation of 6Sb and 8Sb: DmpNH 2 (4.94 mL, 39.3 mmol) added to NEt 3 (5.71 mL, 39.6 mmol) and SbCl 3 (6.23 g, 27.3 mmol) in toluene (110 mL) at 0 uC, stirred for 1.5 h at RT. Filtered and the solvent was removed in vacuo to 5 mL, addition of pentane (5 mL) gave a yellow precipitate after 4 days at 224 uC, which was dissolved in minimal CH 2 Cl 2 and vapour diffusion of pentane gave a mixture of crystals (0.13 g) with two distinct morphologies and colours, manually separated.…”

mentioning

confidence: 99%

“…Filtered and the solvent was removed in vacuo to 5 mL, addition of pentane (5 mL) gave a yellow precipitate after 4 days at 224 uC, which was dissolved in minimal CH 2 Cl 2 and vapour diffusion of pentane gave a mixture of crystals (0.13 g) with two distinct morphologies and colours, manually separated. Pale yellow (, 0.02 g) 6Sb; Crystal Data: 5), 325 (9), 373 (11), 486 (15), 522 (8), 690 (10), 707 (7), 790(3), 811(2), 839(4), 901 (16), 984 (12), 1023 (13), 1097 (6), 1164(1), 1252 (14), 1586 (17), 1799 (19), 1867 (20), 1934 (18); NMR: 1 H (CDCl 3 ): 2.60 (s, 3H), 2.66 (s, 6H), 2.69 (s, 3H), 2.74 (s, 6H), 7.02-7.17…”

mentioning

confidence: 99%