Stanna-<i>closo</i>-dodecaborate Chemistry

and, Torben Gädt; Wesemann, Lars

doi:10.1021/om061042k

Cited by 60 publications

(53 citation statements)

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“…CH, Co͑CO͒ 3 and CH 3 , Mn͑CO͒ 5 can be considered as classical examples of isolobal fragments. Finally, beyond Si, for the isovalent Sn, Gädt and Wesemann 25 have extensively studied stanna-closo-dodecaborate chemistry, considering among others the ͓SnB 11 H 11 ͔ 2− dianion, homologous to ͓1-CB 11 H 12 ͔ 1− monocarbaborate anion, both related to ͑B 12 H 12 ͒ 2− borane. The isolobal analogy pro-vides a mechanism to predict new, hopefully stable, molecules, and compare molecular fragments with each other and with familiar species from organic Chemistry, offering also clues about reactivity and reaction mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Rationalizing and functionalizing stannaspherene: Very stable stannaspherene “alloys”

Zdetsis

2009

The Journal of Chemical Physics

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It is illustrated here by ab initio calculations based on density functional theory and other high level methods that the high stability of the icosahedral Sn(12) (2-) dianion known as stannaspherene, reflects stability toward ionization rather than cohesion. This could be also connected with novel fluxional rearrangements and paths of Sn(12) (1-) leading eventually to Sn(12) (2-) involving charge transfer. In view of the very similar structural and electronic properties with the corresponding isovalent borane (B(12)H(12))(2-), it is demonstrated that stannaspherene can be further rationalized and functionalized on the basis of an isolobal analogy between group 14 clusters and isovalent boranes, carboranes, and bisboranes. Such analogy is of the same nature with analogous isolobal and isovalent similarities between silicon, hydrogenated silicon-carbon clusters and deltahedral boranes and carboranes, which the present author, scoptically and synoptically, has described as the "boron connection." It is predicted and verified theoretically: First, that the isovalent Bi(2)Sn(10) and Sb(2)Sn(10) clusters, considered as the microscopic analogs of tin-bismuth alloys, are very stable (more stable than stannaspherene itself) very symmetric and isolobal to Sn(12) (2-); and second, that embedded clusters of the form M@Sn(12) (2-), M@Bi(2)Sn(10), M=Pt,Pd are very stable and highly symmetrical (I(h) and D(5d) respectively) with large highest occupied-lowest unoccupied molecular orbital gaps and very large embedding energies of the order of 5-6 eV. It is furthermore predicted that Pt@Sn(12) (2-) and Pt@Bi(2)Sn(10) can be synthesized in view of their higher stability compared to Pt@Pb(12) (2-) which has already been synthesized. The marginal energy difference of 0.03 eV between the meta- and the para-isomer of Bi(2)Sn(10) indicates a fluxional behavior with respect to Bi-Sn interchange which should be related with the Sn(12) (1-) fluxionality leading eventually to Sn(12) (2-). This rearrangement is also associated with a strange aromatic behavior. The same type of Bi-Sn fluxionality is also encountered in higher energy structures. Due to the "inert pair effect" in tin, the validity of the isolobal analogy is much stronger and fully valid compared to isovalent species based on germanium or silicon, such as Ge(12) (2-), Bi(2)Ge(10), and Ge(10)C(2)H(2) and Si(12) (2-), Bi(2)Si(10), and Si(10)C(2)H(2). The present ideas are in full agreement with available experiments and suggest even further functionalization of stannaspherene, analogous to metaloboranes, metalocarboranes, and stannaboranes with several potential applications.

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Section: Introductionmentioning

confidence: 99%

Rationalizing and functionalizing stannaspherene: Very stable stannaspherene “alloys”

Zdetsis

2009

The Journal of Chemical Physics

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“…[14] Presumably because of the longer interatomic distances between nickel and tin, a coordination of the fourth cluster is here possible. Values of 2.4761(4) and 2.4706(5) for the Ni-Sn distance were determined.…”

Section: The Homoleptic Complex [Nia C H T U N G T R E N N U N G (Snbmentioning

confidence: 99%

“…The syntheses of homologues of the monoA C H T U N G T R E N N U N G carbaborate anion [1ÀXB 11 H 11 ] 2À (X = Ge, Sn, Pb) was reported for the first time in 1992 by Todd and co-workers. [13] Whereas the coordination chemistry of the tin ligand [SnB 11 H 11 ] 2À has been studied in our group [14] and still is a field of active research, [15] less is known about the nucleophilic behaviour of the germaborate cluster. The methylated derivative [MeGeB 11 H 11 ] À was synthesised by Todd, [13] but no complexes of transition metals have been reported so far.…”

Section: Introductionmentioning

confidence: 99%

Germa‐closo‐dodecaborate: A New Ligand in Transition‐Metal Chemistry with a Strong trans Influence

Dimmer

Schubert

Wesemann

2009

Chemistry A European J

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The strong nucleophilic character of germa-closo-dodecaborate towards late transition metal centres is described. The synthesis and characterisation of the first germa-closo-dodecaborate complexes are presented, and the solid state structures of the germaborate transition metal complexes were determined by X-ray crystal structure analyses. The strong trans influence of the new germaborate ligand was determined by IR spectroscopy and NMR coupling constants.

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“…Komplexe der Form [Ni-(dab)Br 2 ] (dab = 1,4-Diaza-1,3-butadien oder a-Diimin) können im Allgemeinen leicht in der Gegenwart von zusätzlichem dab reduziert werden, wobei sich Komplexe der Zusammensetzung [Ni(dab) 2 ] bilden. [12][13][14] Dabei liegt nach neueren Erkenntnissen das Nickelion in der Oxidationsstufe II vor, die dab-Liganden als negativ geladene Radikale.…”

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“…[12][13][14] Dabei liegt nach neueren Erkenntnissen das Nickelion in der Oxidationsstufe II vor, die dab-Liganden als negativ geladene Radikale. [15][16][17][18] Nach unserem Kenntnisstand wurde das Reduktionsprodukt [Ni(dpp-bian) 2 2 ] isoliert und anhand der 1 H-und 13 C NMR-Spektren identifiziert werden. [12] Dieser Befund wie auch die Reaktionsstöchiometrie von 1:3 stützen die vermutete Oxidation der Nickel(II)-Ausgangsverbindung zur formalen Nickel(IV)-Verbindung zusammen mit einer Reduktion von [Ni(dpp-bian)Br 2 ] (Schema 1).…”

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