Preparation and Properties of a Closo Nitride Cluster, the Cubane [(η-C5Me5)V(μ3-N)]4

Abernethy, Colin D.; Bottomley, Frank; Decken, and Andreas; Cameron, T. Stanley

doi:10.1021/om950947n

Cited by 37 publications

(31 citation statements)

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“…The magnitude of the differences between the wavenumbers of the original absorptions assigned to the V≡N stretching frequencies of 3 and 4 and those of the new absorptions appearing in the spectra of the samples containing 3a and 4a are consistent with the difference in the reduced masses of the two atom pairs (i.e. V≡ 14 N and V≡ 15 N). These results thus serve to confirm the V≡N stretching frequencies in 3 and 4 as 945 and 955 cm -1 , respectively.…”

Section: V≡n Stretching Frequencies Of 3 Andsupporting

confidence: 53%

The synthesis and characterization of [IMesH]+[(η3-C5H5)V(N)Cl2]−: An anionic vanadium(v) complex with a terminal nitrido ligand

et al. 2010

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A series of new half-sandwich vanadium complexes have been prepared. The structures of two new anionic vanadium half-sandwich complexes, [CpVCl(3)](-) and [CpV(N)Cl(2)](-) are presented. (15)N isotopic labelling studies have been conducted to unambiguously assign the V[triple bond, length as m-dash]N infra red stretching frequencies of both a neutral and an anionic (cyclopentadienyl)vanadium nitrido complex. The influence of strongly pi-basic coligands on the hapticity of the cyclopentadienyl ligands in half-sandwich complexes of vanadium is discussed.

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Section: V≡n Stretching Frequencies Of 3 Andsupporting

confidence: 53%

The synthesis and characterization of [IMesH]+[(η3-C5H5)V(N)Cl2]−: An anionic vanadium(v) complex with a terminal nitrido ligand

et al. 2010

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“…[42] The T-shaped arrangement has been described in several complexes containing metal-metal bonds, [4,43] but also in the pentanuclear tantalum complex [{Ta(CH2tBu)2}5(-N)2(3-N)3] [25] (B) or the heterometallic titanium-sodium derivative [{Ti(iPrtren)}2(3-N)Na(thf)] (iPrtren = N(CH2CH2NiPr2)3) [44] . Lastly, the pyramidal geometry has been found in early transition metal complexes such as the trinuclear derivative [{TiCp*(-NH)}3(3-N)] [45] (C) or the cube-type tetranuclear species [(MCp*)4(3-N)4] (M = Ti (D), [46] V [47] ), as well as in the Group 8 clusters [(RuCp*)3(3- 1 : 3 : 1 -CHC6H4)(-H)(3-N)] [48] and [Fe3( tbs L)(3-N)] -( tbs L = 1,3,5-C6H9(NHPh-o-NSitBuMe2)3) [49] . Scheme 3.…”

Section: Structure and Bonding Modesmentioning

confidence: 97%

Heterometallic Cube‐Type Molecular Nitrides

2016

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Polynuclear transition metal nitrido complexes constitute a class of molecular cage compounds with fascinating structures and interesting bonding properties. However, there is a lack of systematic strategies for the rational construction of aggregates with desired structure and composition. This article provides a brief overview of the structure and bonding modes of polynuclear nitrido complexes, the most common synthetic approaches used to generate such aggregates, and a systematic review of the development of a family of heterometallic nitrido complexes with [MTi3N4] cube-type cores. The rational entry to those well-defined systems is based on the incorporation of transition, lanthanides, and main-group metals into the incomplete cube structure of the trinuclear titanium(IV) imido-nitrido complex [{TiCp*(-NH)}3(3-N)] (Cp* =  5 -C5Me5). The great versatility of [{TiCp*(-NH)}3(3-N)] as a preorganized metalloligand is also confirmed by the possibility of preparing complexes with heterometals in low (e.g. Mo 0 , Ir I and Pt 0 ) or high oxidation states (e.g. Zr IV , Ta V and Pt IV ).

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“…Complexes 01 (Figure c) to 03 have (V 2 ) 4+ cores with R MM values ranging from 2.399 to 2.563 Å (Berno and Gambarotta, Howard and co-workers, Haddad et al) while structure 04 has a short V–V distance of 2.324 Å (Buijink). The cluster 05 has a cubanelike center with four vanadium atoms, each pair separated by 2.674 Å (Abernethy), while structure 06 has a bridging azide ligand and an R MM value of 2.563 Å − ), and R MM values ranging from 2.640 to 2.857 Å, which are longer than those in this list with imido or nitrido ligands.…”

Section: Vanadium–vanadium Bondsmentioning

confidence: 97%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

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This survey of metal–metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) n+, (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. The combination of experimental and computational results leads us to propose for the first time the ranges and “best” estimates for MM bond distances of all types (Ti–Ti through Zn–Zn, single through quintuple).

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Preparation and Properties of a Closo Nitride Cluster, the Cubane [(η-C₅Me₅)V(μ₃-N)]₄

Cited by 37 publications

References 13 publications

The synthesis and characterization of [IMesH]+[(η3-C5H5)V(N)Cl2]−: An anionic vanadium(v) complex with a terminal nitrido ligand

The synthesis and characterization of [IMesH]+[(η3-C5H5)V(N)Cl2]−: An anionic vanadium(v) complex with a terminal nitrido ligand

Heterometallic Cube‐Type Molecular Nitrides

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

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