Remarkable properties of four-, five-, and six-membered diboraheterocycles

Siebert, W.

doi:10.1351/pac198759080947

Cited by 45 publications

(9 citation statements)

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“…9,12,13 The results reported here now demonstrate the viability of the principle of the stepwise synthesis of macromolecular heteroborane cluster species that have more intimate subcluster fusion linkages.Contribution no. 46 from the Rei-Leeds Anglo-Czech Polyhedral Collaboration (ACPC).…”

mentioning

confidence: 57%

Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S₂B₁₆H₁₆]

Jelı́nek¹,

Kennedy²,

Štı́br³

1994

J. Chem. Soc., Chem. Commun.

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confidence: 57%

Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S₂B₁₆H₁₆]

Jelı́nek¹,

Kennedy²,

Štı́br³

1994

J. Chem. Soc., Chem. Commun.

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“…The insertion of unsaturated organic compounds into metal−carbon bonds is a well-known process that is an important step in a many stoichiometric and catalytic transformations. Since the C 2 B 3 fragment is highly stabilizing toward a variety of metal centers, ,− we anticipated that discrete insertion steps could be easily studied using (carborane)CpTaR 2 and related systems.…”

Section: Discussionmentioning

confidence: 99%

Insertion Reactions of Tantalum(V) Carborane Alkyl and Aryl Complexes with Nitriles and Isonitriles. Thermal and Photochemical Isomerization of η²-Iminoacyl Isomers¹

et al. 1997

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Tantalum carborane complexes (Et2C2B4H4)CpTaR2 (R = Me, Ph) undergo insertion reactions with nitriles and isonitriles under conditions that differ from formally isoelectronic metallocene compounds of group 4 metals. The dimethyltantalum system requires UV−vis irradiation, whereas the diphenyltantalum complex generally reacts at elevated temperatures. Although insertions of isonitriles into metal−alkyl bonds have been reported in a wide variety of cases, there are very few examples of stable isomeric η2-iminoacyl intermediates that can be isolated and completely converted from one form into the other. Two such cases are reported here, including the X-ray crystallographic analysis of both isomers of (Et2C2B4H4)CpTaCH3(η2-C,N-C{N-t-Bu}CH3) (5a,5b) and one isomer of (Et2C2B4H4)CpTaCH3(η2-C,N-C{N(2,6-Me2C6H3)}C6H5) (7a). Photochemical isomerization of 7a, followed by exposure to an additional equivalent of isocyanide, resulted in a novel cage-insertion reaction to give [(Et2C2B4H3(C6H5)(CHN(2,6-Me2C6H3))]CpTa(η2-C,N-C{N(2,6-Me2C6H3)}C6H5) (8), the crystal structure of which was also determined. Stereoelectronic and steric factors that may contribute to the thermodynamic stability of N-out isomers of η2-iminoacyl complexes are suggested, and data indicating the relatively electron-rich nature of the (carborane)(Cp)TaVR2 fragment is identified.

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“…165 Metallacarboranes derived from tricarbon carboranes have not been explored in great detail with the exception of Siebert's work on diborolene. [134][135][136] The low-yield syntheses of the tricarbaboranes restricted their synthetic utility in the production of the corresponding metallatricarbaborane complexes.166 167 The most recent report from Sneddon's group on the improved and high-yield (ca. 80 %) synthesis of the monoanionic ligand [6-CH3-5,6,8-C3B7H9]-and its subsequent conversion to a neutral precursor, rado-6-CH3-5,6,9-C3B7Hio, has given hope for the rapid development of this area of metallacarborane chemistry.…”

Section: Complexes Of Arene and C8h82-ligandsmentioning

confidence: 99%

Recent advances in the chemistry of carborane metal complexes incorporating d- and f-block elements

Saxena¹,

Hosmane²

1993

Chem. Rev.

236

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Remarkable properties of four-, five-, and six-membered diboraheterocycles

Abstract: Abstract

Cited by 45 publications

References 0 publications

Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S₂B₁₆H₁₆]

Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S₂B₁₆H₁₆]

Insertion Reactions of Tantalum(V) Carborane Alkyl and Aryl Complexes with Nitriles and Isonitriles. Thermal and Photochemical Isomerization of η²-Iminoacyl Isomers¹

Recent advances in the chemistry of carborane metal complexes incorporating d- and f-block elements

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Remarkable properties of four-, five-, and six-membered diboraheterocycles

Abstract: Abstract

Cited by 45 publications

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Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S2B16H16]

Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S2B16H16]

Insertion Reactions of Tantalum(V) Carborane Alkyl and Aryl Complexes with Nitriles and Isonitriles. Thermal and Photochemical Isomerization of η2-Iminoacyl Isomers1

Recent advances in the chemistry of carborane metal complexes incorporating d- and f-block elements

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Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S₂B₁₆H₁₆]

Macropolyhedral boron-containing cluster chemistry. Cluster fusion to give the novel nido–nido eighteen-vertex dithiaoctadecaborane (anti)-[9,9′-S₂B₁₆H₁₆]

Insertion Reactions of Tantalum(V) Carborane Alkyl and Aryl Complexes with Nitriles and Isonitriles. Thermal and Photochemical Isomerization of η²-Iminoacyl Isomers¹