Metallaboranes

Barton, Lawrence; Srivastava, D. K.

doi:10.1016/b978-008046519-7.00008-3

Cited by 53 publications

(56 citation statements)

References 287 publications

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“…Also present in the 1 H NMR spectrum are signals due to the three dimethylphenylphosphine ligands and the two hydrides on the tungsten. Spin saturation transfer experiments performed on (1) show exchange between the W-H-B bridges and the W-H hydrides at room temperature.…”

Section: Resultsmentioning

confidence: 99%

“…Compound (1) has been characterised by multi-nuclear NMR spectroscopy and elemental analysis as nido-2-[W(PMe 2 Ph) 3 H 2 B 4 H 8 ] (Fig. 1).…”

Section: Resultsmentioning

confidence: 99%

“…The reaction of pentaborane(9) (nido-B 5 H 9 ) with transition-metal compounds or the ½nido À B 5 H À 8 anion with transition-metal chlorides gives a wide variety of metallaborane structures [1][2][3][4]. We are exploring the reaction of pentaborane (9) with electron-rich transition-metal compounds.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of pentaborane(9) with electron-rich molybdenum and tungsten phosphine polyhydrides

Green¹,

Walker²,

Mountford³

et al. 2006

Journal of Organometallic Chemistry

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Section: Resultsmentioning

confidence: 99%

“…Compound (1) has been characterised by multi-nuclear NMR spectroscopy and elemental analysis as nido-2-[W(PMe 2 Ph) 3 H 2 B 4 H 8 ] (Fig. 1).…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Reactions of pentaborane(9) with electron-rich molybdenum and tungsten phosphine polyhydrides

Green¹,

Walker²,

Mountford³

et al. 2006

Journal of Organometallic Chemistry

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“…All of these metallaboranes are made from pentaborane(9) or ½B 5 H À 8 anion precursor and usually have a plane of symmetry [11][12][13]. Another ruthenaborane example is nido-2-[Ru(CO)(PPh 3 ) 2 B 5 H 9 ] which is thermally unstable at room temperature decomposing to nido-2-[Ru(CO)(PPh 3 ) 2 B 4 H 8 ] [24].…”

Section: Resultsmentioning

confidence: 99%

Reactions of small boranes with ruthenium phosphine hydrides: Oligomerisation of monoborane-tetrahydrofuran to a nido-hexaruthenaborane

Green¹,

Leach²,

Kelland³

2006

Journal of Organometallic Chemistry

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“…The redox flexibility of transition-element centres allied with the closo-nido-arachno-etc redox flexibility of boron-containing cluster structures engenders much interesting metallaborane structural, behavioural, and reaction chemistry [1,2]. Rhodium and iridium metallaboranes have figured significantly in this regard, for example in terms of reactions, both catalytic and non-catalytic [3][4][5][6][7][8][9], in phenomena such as fluxionalities [10,11], and in the establishment of interesting cluster types, such as those of 'isocloso' and 'isonido' geometries [12][13][14][15].…”

Section: ____________________________________________________________mentioning

confidence: 99%

Macropolyhedral boron-containing cluster chemistry: two-electron variations in intercluster bonding intimacy. Contrasting structures of 19-vertex [(η5-C5Me5)HIrB18H19(PHPh2)] and [(η5-C5Me5)IrB18H18(PH2Ph)]

Shea¹,

Jelı́nek²,

Perera³

et al. 2004

Inorganica Chimica Acta

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_________________________________________________________________________________________The redox flexibility of transition-element centres allied with the closo-nido-arachno-etc redox flexibility of boron-containing cluster structures engenders much interesting metallaborane structural, behavioural, and reaction chemistry [1,2]. Rhodium and iridium metallaboranes have figured significantly in this regard, for example in terms of reactions, both catalytic and non-catalytic [3][4][5][6][7][8][9], in phenomena such as fluxionalities [10,11], and in the establishment of interesting cluster types, such as those of 'isocloso' and 'isonido' geometries [12-15]. Single-cluster borane, heteroborane and metallaborane chemistry is governed at present by an uppermost limit to cluster size of about fourteen vertices [16,17]: to extend beyond this horizon the clusters need to be linked or fused together to make bigger cluster assemblies. Intimate intercluster fusions, with two or more atoms held in common between the constituent subclusters, result in so-called 'macropolyhedral' species [18][19][20][21], in which the multicentre bonding characteristics of boron extend across the nexus between the constituent subclusters. The structural flexibility resulting from the incorporation of rhodium and iridium centres in macropolyhedral metallaborane assemblies has been most useful in the development of this macropolyhedral area [22][23][24][25][26][27][28][29] The addition of electrons to the cluster in a single-cluster compound generally results in cluster opening along the closo-nido-arachno-etc sequence; conversely, removal of electrons generally results in cluster closure [30].In macropolyhedral boron-containing cluster compounds, in which single clusters are fused together, the addition or removal of electrons can, alternatively, result in a decease or an increase, respectively, in the degree of intimacy of intercluster fusion, rather than the opening or closing of individual subclusters [6,18,20,29]. For the development and understanding of intercluster fusion chemistry, there is merit in establishing systems in which such alternative behaviours can be observed and defined. . In compound 1, the cluster structure (schematic I A) is that of a nido twelve-vertex {IrB 11 } unit fused with a nido ten-vertex {B 10 } unit, with three boron atoms held in common (schematic I B). By contrast, in compound 2, the cluster structure (schematic II A) is that of a nido eleven-vertex {IrB 10 } unit fused with a nido ten-vertex {B 10 } unit, but now with only two boron atoms held in common (schematic II B). In the overall formation of 8 from 1 , the two-electron gain associated with the incorporation of the PH 2 Ph ligand is cancelled by the two-electron loss associated with the elimination of dihydrogen (equation 2, where L is PH 2 Ph ); overall, the three-atoms-in-common configuration is thence retained, and the individual subclusters retain their individual nido characters. The observations involving the conversion of rhodium compound 4 ...

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Metallaboranes

Cited by 53 publications

References 287 publications

Reactions of pentaborane(9) with electron-rich molybdenum and tungsten phosphine polyhydrides

Reactions of pentaborane(9) with electron-rich molybdenum and tungsten phosphine polyhydrides

Reactions of small boranes with ruthenium phosphine hydrides: Oligomerisation of monoborane-tetrahydrofuran to a nido-hexaruthenaborane

Macropolyhedral boron-containing cluster chemistry: two-electron variations in intercluster bonding intimacy. Contrasting structures of 19-vertex [(η5-C5Me5)HIrB18H19(PHPh2)] and [(η5-C5Me5)IrB18H18(PH2Ph)]

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