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Abarca, Angel; Galakhov, Mikhail; Gómez‐Sal, Pilar; Martı́n, Avelino; Mena, Miguel; Poblet, Josep M.; Santamarı́a, Cristina; Sarasa, José Pedro

doi:10.1002/(sici)1521-3757(20000204)112:3<544::aid-ange544>3.3.co;2-e

Cited by 19 publications

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“…This trigonal antiprism environment for the molybdenum central atom is similar to that reported by us [4], although the change of the m 3 -ethylidyne by the apical m 3 -nitrido leads to an average TieO distance 0.04 Å longer. On the other hand, TieN bond distances are only 0.03 Å longer than that found in the parent compound 1 [12].…”

Section: Coordination Of [{Ticontrasting

confidence: 64%

“…In fact, thermal or photochemical treatments of the alkylidyne oxocomplexes with [M(CO) 6 ] compounds, to check if those organometallic ligands were able to displace three carbonyl groups from the group 6 metal atom coordination sphere, led to an intractable mixture of unidentified compounds. On the other hand, irradiation was necessary to perform successfully the same reaction with the imidoenitrido derivative [4]. Table 1 Selected distances (Å) and angles ( ) for complex 3.…”

Section: Reaction Of [{Timentioning

confidence: 83%

“…Along with their ability to act as tridentate ligands through the oxygen atoms, these systems present very similar characteristics to the metallacrown molecules described by Pecoraro et al [3]. As result of the treatment of these oxocompounds with the labile complex [Mo(CO) 3 (1,3,5-Me 3 C 6 H 3 )], we reported the formation and structure of the heterometallocubanes [{(CO) 3 Mo}(m 3 -O) 3 {Ti 3 (h 5 -C 5 Me 5 ) 3 (m 3 -CR)}] (R ¼ H, Me) [4], in which the molybdenum tricarbonyl moiety is linked to three bridging oxygen atoms. This reaction provided the starting point of an unprecedented chemistry based on using of these titanium derivatives as macrocyclic tripodal O 3 -ligands [5,6].…”

Section: Introductionmentioning

confidence: 99%

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Discovering the chemical reactivity of the molecular oxonitride [{Ti(η5-C5Me5)(μ-O)}3(μ3-N)]

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Carbó

Moral

et al. 2011

Journal of Organometallic Chemistry

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Section: Coordination Of [{Ticontrasting

confidence: 64%

Section: Reaction Of [{Timentioning

confidence: 83%

Section: Introductionmentioning

confidence: 99%

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Discovering the chemical reactivity of the molecular oxonitride [{Ti(η5-C5Me5)(μ-O)}3(μ3-N)]

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Carbó

Moral

et al. 2011

Journal of Organometallic Chemistry

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“…The analysis of the molecular orbitals shows that all these clusters have eight metallic electrons localized on the Group 9 element. As in the previously studied hetero- [10] and homometallocubanes [20] the LUMO is a bonding combination of titanium d orbitals, stressing that the formation of the azametallocubane is not accompanied by an oxidation of the Group 9 element. However, the molecular orbital (MO) composition given in Table 3 shows that there is a non-negligible mixing between rhodium (or iridium) and titanium d orbitals.…”

Section: Resultssupporting

confidence: 88%

“…In agreement with the electronic sharing for larger metals in the iridium complexes, the dissociation energy to give the {M(cod)} incomplete-cube fragments is computed to be 444.7 kJ mol À1 for 5', 66 kJ mol À1 above that of 4'. These values are not very different from those computed for d 0 ± d 6 complexes, [10] which range between 350 ± 445 kJ mol À1 .…”

Section: Resultsmentioning

confidence: 65%

Rhodium/Iridium-Titanium Azaheterometallocubanes

et al. 2001

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Treatment of [[Ti(eta5-C5Me5)(mu-NH)]3(mu3-N)] (1) with the diolefin complexes [[MCl(cod)]2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) in toluene afforded the ionic complexes [M-(cod)(mu3-NH)3Ti3(eta5-C5Me5)3(mu3-N)]Cl [M = Rh (2), Ir (3)]. Reaction of complexes 2 and 3 with [Ag(BPh4)] in dichloromethane leads to anion metathesis and formation of the analogous ionic derivatives [M(cod)(mu3-NH)3Ti3-(eta5-C5Me5)3(mu3-N)][BPh4] [M = Rh (4), Ir (5)]. An X-ray crystal structure determination for 5 reveals a cube-type core [IrTi3N4] for the cationic fragment, in which 1 coordinates in a tripodal fashion to the iridium atom. Reaction of the diolefin complexes [[MCl(cod))2] (M = Rh, Ir) and [[RhCl(C2H4)2]2] with the lithium derivative [[Li(mu3-NH)2(mu3-N)-Ti3(eta5-C5Me5)3(mu3-N)]2] x C7H8 (6 C7H8) in toluene gave the neutral cube-type complexes [M(cod)(mu-NH)2(mu3-N)Ti3-(eta5-C5Me5)3(mu3-N)] [M = Rh (7), Ir (8)] and [Rh(C2H4)2(mu3-NH)2(mu3-N)Ti3(eta5-C5Me5)3(mu3-N)] (9), respectively. Density functional theory calculations have been carried out on the ionic and neutral azaheterometallocubane complexes to understand their electronic structures.

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[{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]: An Efficient Entry to Single and Double Cube-Type Nitrido Complexes

et al. 2000

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Group 4 tetrametallic derivatives of the formula [(ML n ) 4 (m 3 -E) 4 ] with cube-type cores remain extremely rare and are limited to halide-bridged [{TiL} 4 (m 3 -Cl) 4 ] (L h 8 -C 8 H 8 , [1] Me 3 [2] ), chalcogenide-bridged [{Ti(h 5 -C 5 H 4 R)} 4 (m 3 -S) 4 ], [3] and imido-bridged [{Ti(h 5 -C 5 H 5 )} 4 (m 3 -NSnMe 3 ) 4 ] complexes. [4] Our first contributions in this field were the preparation of the singular nitrido and alkylidyne complexes [{Ti(h 5 -C 5 Me 5 )(m 3 -E)} 4 ] (E N [5] , CH [6] ), which contained an almost perfect Ti 4 E 4 cube. A possible synthetic strategy to access this type of compounds would involve the incorporation of different metal complex fragments in a cuboidal core such as [Ti 3 (m-NH) 3 (m 3 -N)], [7] in a similar way to that reported for [M 3 (m-S) 3 (m 3 -S)] species. [8±10] In this context, we have recently determined that the preorganized [11] ªorganometallic ligandº 1 is able to displace mesitylene or carbonyl ligands in [{Ti(h 5 6 ], respectively, [12] and also reacts, by NÀH activation, with tris(dimethylamido)cyclopentadienyltitanium(iv) compounds [13] to give azametallocubane complexes. Herein we describe the reactions of 1 with several d 0 imido-and amidotitanium and -zirconium com-plexes that yield new cube-type derivatives and, for the first time, metal corner-shared double cube nitrido complexes. This synthetic method should be generally applicable and thus make the Ti 3 N 4 core a very versatile building block for heterometal cluster chemistry and for molecular precursors of new ternary nitrides MTi x N y . Reaction of complex 1 with [Ti(NAr)Cl 2 (py) 3 ] (Ar 2,4,6-C 6 H 2 Me 3 ) [14] in toluene at room temperature results in displacement of the pyridine (py) ligands and formation of 2´(C 7 H 8 ) in 51 % yield (Scheme 1). Analogous treatment of 1 with the tert-butylimido derivative [Ti(NtBu)Cl 2 (py) 3 ] [14] in toluene afforded the complex 3 as a green precipitate in 82 % [Ti(NAr)Cl 2 {(m 3 -NH) 2 Ti 3 (h 5 -C 5 Me 5 ) 3 (m-NH)(m 3 -N)}]´(C 7 H 8 ) 2´(C 7 H 8 ) [TiCl 2 {(m 3 -N) 3 (m 3 -NH)Ti 3 (h 5 -C 5 Me 5 ) 3 }] 3yield. [15] The addition of 2,4,6-trimethylaniline (1 equiv) to a solution of 3 in CDCl 3 at room temperature gave 2 within several days. Complexes 2 and 3 were characterized by spectral and analytical methods, as well as by an X-ray structure determination in the case of 2 (vide infra).[Ti] HN [Ti] NH [Ti] HN N Ti RN Cl Cl [Ti] N H NH [Ti] N H N [Ti] [Ti] N [Ti] NH [Ti] N N Cl Ti Cl 3 [Ti(NR)Cl 2 (py) 3 ] NH 2 Ar, CDCl 3 1 20°C, -3 py R = tBu, 20°C, -NH 2 tBu R = 2,4,6-C 6 H 2 Me 3 2 R = tBu 2a Scheme 1. Synthesis of 2 and 3 from 1. [Ti] Ti(h 5 -C 5 Me 5 ).Treatment of 1 with tetrakis(dimethylamido)titanium(iv) or -zirconium(iv) in toluene at 150 8C afforded the corner-shared double cube complexes 4´2 C 7 H 8 and 5´1.5 C 7 H 8 , respec-[Ti{(m 3 -N) 3 (m 3 -NH)Ti 3 (h 5 -C 5 Me 5 ) 3 } 2 ]´2 C 7 H 8 4´2 C 7 H 8 [Zr{(m 3 -N) 3 (m 3 -NH)Ti 3 (h 5 -C 5 Me 5 ) 3 } 2 ]´1.5 C 7 H 8 5´1.5 C 7 H 8 tively, as dark green crystals in 69 and 60 % yield, resp...

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Cited by 19 publications

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Discovering the chemical reactivity of the molecular oxonitride [{Ti(η5-C5Me5)(μ-O)}3(μ3-N)]

Discovering the chemical reactivity of the molecular oxonitride [{Ti(η5-C5Me5)(μ-O)}3(μ3-N)]

Rhodium/Iridium-Titanium Azaheterometallocubanes

[{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)]: An Efficient Entry to Single and Double Cube-Type Nitrido Complexes

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