Icosahedra with slipped vertexes. Influence of electron donation on the geometry of a stannadicarbadodecaborane (stannacarborane)

Jutzi, Peter; Galow, Peter; Abu‐Orabi, Sultan T.; Arif, Atta M.; Cowley, Alan H.; Norman, Nicholas C.

doi:10.1021/om00148a021

Cited by 47 publications

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“…While only one cage geometry of each of the closo systems, the [SnB n H n ] 2-dianions and the [SnCB n H n+1 ] -anions, is known, there are many different geometries of SnC 2 B n H n+2 clusters with n = 4, 8, 9 and 10 reported in the literature (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24). Molecular structures of dicarbastannaboranes with n = 4 and n = 10 have been structurally characterised (13,15,18,22) and optimised geometries for each system are in very good agreement with experimental data (Table 1).…”

Section: Resultsmentioning

confidence: 99%

“…The lack of -donating ability of the SnC 2 B 4 H 6-n R n systems was ascribed to the diffuse nature of the exo-polyhedral lone-pair on the tin center (19) and to the symmetric electron distribution in some of the lower lying filled M.O.s which the authors associated with the Sn 'lone pair' (15 -, a stronger -donor and weaker -acceptor than CO or PF 3 . We also report the shapes, energies and atomic compositions of the orbitals for these systems as well as for related dicarbastannaboranes (13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24).…”

Section: Introductionmentioning

confidence: 99%

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DFT studies of the σ-donor/π-acceptor properties of [SnCB₁₀H₁₁]^– and its relationship to [SnCl₃]^–, CO, PF₃, [SnB₁₁H₁₁]^2–, SnC₂B₉H₁₁, and related SnC₂B_nH_n+2 compounds

Fox¹,

Marder²,

Wesemann³

2009

Can. J. Chem.

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Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. -, a stronger -donor and weaker -acceptor than CO or PF 3 . The non-carbon containing cluster [SnB 11 H 11 ] 2-is shown to be a very strong donor, whereas the dicarbon cluster 3,1,2-SnC 2 B 9 H 11 is a poor -donor but good Lewis acid, consistent with experimental results. Thus, these systems can be tuned across a very wide range via isolobal replacement of [BH] -for CH vertices. The higher negative charge in the non-carbon containing systems, as well as the fact that boron is more electropositive than carbon, contribute to the increased energies of both HOMO and LUMO in the stannaboranes compared with the stannacarboranes, explaining their relative donor and acceptor properties.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

DFT studies of the σ-donor/π-acceptor properties of [SnCB₁₀H₁₁]^– and its relationship to [SnCl₃]^–, CO, PF₃, [SnB₁₁H₁₁]^2–, SnC₂B₉H₁₁, and related SnC₂B_nH_n+2 compounds

Fox¹,

Marder²,

Wesemann³

2009

Can. J. Chem.

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“…The dianionic salts of the nido-carboranes [C 2 B 9 H 11 ] 2± and [C 2 B 4 H 6 ] 2± react with SnCl 2 and PbCl 2 under the formation of the respective closo-metallacarboranes EC 2 B 9 H 11 , EC 2 B 4 H 6 (E = Pb, Sn) [5,6]. In these closo-clusters the group IV element carries no exo polyhedral substituent and donates two electrons to the cage bonding.…”

Section: Introductionmentioning

confidence: 99%

Coordination of acloso-Cluster at Rhodium and Iridium

Marx

Wesemann

Dehnen

2001

Z. anorg. allg. Chem.

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Stanna-closo-dodecaborate [Bu 3 MeN] 2 [SnB 11 H 11 ] reacts as a nucleophile with the rhodium and iridium electrophiles of type [Cp*M(bipy')Cl][BF 4 ] under formation of a transition metal tin bond. The zwitterionic molecules [Cp*M(bipy')(SnB 11 H 11 )] (with M = Rh, Ir) were characterized by NMR spectroscopy, elemental analyses and X-ray crystal structure analyses. A high dipole moment of 25.67 D was calculated by DFT methods in the case of the rhodium derivative. Koordination eines closo-Clusters an Rhodium und Iridium Inhaltsu È bersicht. Der Stanna-closo-dodecaboratcluster [Bu 3 MeN] 2 [SnB 11 H 11 ] reagiert mit den Ûbergangsmetall-elektrophilen [Cp*M(bipy')Cl][BF 4 ] von Rhodium und Iridium unter Bildung einer Zinn±Metall Bindung. Die zwitterionischen Reaktionsprodukte [Cp*M(bipy')(SnB 11 H 11 )] (mit M = Rh, Ir) wurden durch NMR-Spektroskopie, Elementaranalysen sowie Kristallstrukturbestimmungen charakterisiert. Im Fall der Rhodiumverbindung wurde ein Dipolmoment von 25.67 D durch DFT Methoden berechnet.

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“…Similar Lewis-acid behavior and attendant distortions were found in the larger cage, closo-MC 2 B 9 metallacarboranes. 9b, 17 The Lewis acidbase behavior of the commo-M(IV) complexes is not straightforward. Hawthorne and co-workers studied the reaction of commo-3,3′-Si(3,1,2-SiC 2 B 9 H 11 ) 2 with several Lewis bases.…”

Section: Introductionmentioning

confidence: 99%

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 25. Syntheses, Structures, and Reactivities of GeCl₃-Substituted Half-Sandwich Germacarboranes, closo-1-Ge-2-(SiMe₃)-3-(R)-5-(GeCl₃)-2,3-C₂B₄H₃ (R = SiMe₃, Me, and H)

Hosmane

Yang

et al. 1998

Organometallics

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Anhydrous GeCl4 reacts with the closo-stannacarboranes 1-Sn-2-(SiMe3)-3-(R)-2,3-C2B4H4 (R = SiMe3 (I), Me (II), and H (III)) in the absence of solvents to give the corresponding closo-germacarboranes 1-Ge-2-(SiMe3)-3-(R)-5-(GeCl3)-2,3-C2B4H3 (R = SiMe3 (IV), Me (V), and H (VI)) in yields of 43%, 22%, and 51%, respectively. Despite the presence of two potential Lewis-acid sites, the reactions of the germacarboranes with the bases C10H8N2, C8H6N4, and C15H11N3 produced exclusively 1-(L)-2-(SiMe3)-3-(R)-5-(GeCl3)-1,2,3-GeC2B4H3 (L = C10H8N2, R = SiMe3 (VII) and Me (VIII); L = C15H11N3, R = SiMe3 (XI)) or, when L = C8H6N4, the bridged complexes 1,1‘-(2,2‘-C8H6N4)-[1-Ge-2-(SiMe3)-3-(R)-5-(GeCl3)-2,3-C2B4H3]2 (R = SiMe3 (IX), Me (X)). The reaction of IV with (η5-C5H5)Fe(η5-C5H4CH2(Me)2N) produced a 1:1 mixture of the salt {[(η5-C5H5)Fe(η5-C5H4CH2]2N(Me)2}+{GeCl3}- (XII) and 1-Ge[(η5-C5H5)Fe(η5-C5H4CH2(Me)2N)]-2,3-(SiMe3)2-5-(NMe2)-2,3-C2B4H3 (XIII), a germacarborane in which a NMe2 group replaced the GeCl3 moiety on the carborane cage. All compounds were characterized by their infrared and 1H, 11B, and 13C NMR spectra, as well as chemical analysis. In addition, IV−VII, IX, and XII were characterized by single-crystal X-ray diffraction. The structures showed IV−VI to be half-sandwich complexes in which a Ge(II) was symmetrically bound to the C2B3 faces of the carboranes, with a Ge(IV) terminally bonded to the unique borons of the cages in a GeCl3 group. The structures of the Lewis-base adducts, VII and IX, showed that the nitrogens of the bases were symmetrically bonded to the Ge(II) atoms. Coordination by the bases resulted in a slip distortion of the capping metal atoms toward the boron side of the cages. Compounds XII and XIII are the final products of a sequence of reactions, one of which involves the displacement of a [GeCl3]- unit from the unique boron by a (η5-C5H5)Fe(η5-C5H4CH2(Me)2N) base, producing an intermediate that reacts further with another molecule of the base to give both XII and XIII. In no case was there any evidence of the Ge(IV) acting as a reactive Lewis-acid center. Ab initio molecular orbital calculations were used in rationalizing some of the synthetic and spectroscopic results obtained in this study.

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Icosahedra with slipped vertexes. Influence of electron donation on the geometry of a stannadicarbadodecaborane (stannacarborane)

Cited by 47 publications

References 0 publications

DFT studies of the σ-donor/π-acceptor properties of [SnCB₁₀H₁₁]^– and its relationship to [SnCl₃]^–, CO, PF₃, [SnB₁₁H₁₁]^2–, SnC₂B₉H₁₁, and related SnC₂B_nH_n+2 compounds

DFT studies of the σ-donor/π-acceptor properties of [SnCB₁₀H₁₁]^– and its relationship to [SnCl₃]^–, CO, PF₃, [SnB₁₁H₁₁]^2–, SnC₂B₉H₁₁, and related SnC₂B_nH_n+2 compounds

Coordination of acloso-Cluster at Rhodium and Iridium

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 25. Syntheses, Structures, and Reactivities of GeCl₃-Substituted Half-Sandwich Germacarboranes, closo-1-Ge-2-(SiMe₃)-3-(R)-5-(GeCl₃)-2,3-C₂B₄H₃ (R = SiMe₃, Me, and H)

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Icosahedra with slipped vertexes. Influence of electron donation on the geometry of a stannadicarbadodecaborane (stannacarborane)

Cited by 47 publications

References 0 publications

DFT studies of the σ-donor/π-acceptor properties of [SnCB10H11]– and its relationship to [SnCl3]–, CO, PF3, [SnB11H11]2–, SnC2B9H11, and related SnC2BnHn+2 compounds

DFT studies of the σ-donor/π-acceptor properties of [SnCB10H11]– and its relationship to [SnCl3]–, CO, PF3, [SnB11H11]2–, SnC2B9H11, and related SnC2BnHn+2 compounds

Coordination of acloso-Cluster at Rhodium and Iridium

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 25. Syntheses, Structures, and Reactivities of GeCl3-Substituted Half-Sandwich Germacarboranes, closo-1-Ge-2-(SiMe3)-3-(R)-5-(GeCl3)-2,3-C2B4H3 (R = SiMe3, Me, and H)

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DFT studies of the σ-donor/π-acceptor properties of [SnCB₁₀H₁₁]^– and its relationship to [SnCl₃]^–, CO, PF₃, [SnB₁₁H₁₁]^2–, SnC₂B₉H₁₁, and related SnC₂B_nH_n+2 compounds

DFT studies of the σ-donor/π-acceptor properties of [SnCB₁₀H₁₁]^– and its relationship to [SnCl₃]^–, CO, PF₃, [SnB₁₁H₁₁]^2–, SnC₂B₉H₁₁, and related SnC₂B_nH_n+2 compounds

Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 25. Syntheses, Structures, and Reactivities of GeCl₃-Substituted Half-Sandwich Germacarboranes, closo-1-Ge-2-(SiMe₃)-3-(R)-5-(GeCl₃)-2,3-C₂B₄H₃ (R = SiMe₃, Me, and H)