Convergent syntheses of [Sn7{C6H3-2,6-(C6H3-2,6-iPr2)2}2]: a cluster with a rare pentagonal bipyramidal motif

Rivard, Eric; Steiner, Jochen; Fettinger, James C.; Giuliani, Jason R.; Augustine, Matthew P.; Power, Philip P.

doi:10.1039/b709446a

Cited by 79 publications

(89 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[1][2][3][4][5][6][7][8][9][10] Such functionalization can be usually accomplished through the methods and techniques of organometallic Chemistry for these materials directly or indirectly through isoelectronic and other analogies ͑such as the isolobal analogy͒ 11 to well known and well studied "similar materials." In addition to carbon, silicon and mixed carbonsilicon nanostructures, nanosystems, and cluster composed structures, germanium, tin, and ͑less so͒ lead, can form many functional and important nanostructures which can be further functionalized.…”

Section: Introductionmentioning

confidence: 99%

Rationalizing and functionalizing stannaspherene: Very stable stannaspherene “alloys”

Zdetsis

2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 99%

Rationalizing and functionalizing stannaspherene: Very stable stannaspherene “alloys”

Zdetsis

2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…The Mo1eMo2 distance in the pentagon is 2.7603(4) Å, while the internal angles within this pentagon are in the range of 88.70(11) to 129.4(2) (107.94 average), slightly less than the expected value (108 ) for a pentagonal planar geometry [31]. All of the MoeB and BeB distances are in the normal range like other molybdaborane clusters [32].…”

Section: Isolation and Structural Characterization Of 6 Andmentioning

confidence: 91%

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Ponniah

Bharathan

Bose

et al. 2012

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…[30] [31,32] Überraschenderweise gibt es nur wenige Studien zur Chemie dieses Stannylens (Schema 1), das sowohl mit Wasser und Alkoholen [33] als auch mit Alkyl-Aluminium-, Alkyl-Gallium- [34] und Alkyl-Zink-Verbindungen [35] reagiert, aber nicht mit weißem Phosphor. [36] Hier berichten wir über die Reaktivitätv [41] gemessene Bindungslängen liegen zwischen 2.7685(2) und 3.5496-(9) ), [42][43][44][45][46] aber eine NBO-Analyse zeigt keine kovalente Sn-Sn-Bindung. [47] Der kleine Sn-Sn-Abstand impliziert jedoch eine Wechselwirkung zwischen Sn1 und Sn2.…”

unclassified

Eine monoanionische Arsenid‐Quelle: Decarbonylierung des 2‐Arsaethinolat‐Anions bei der Reaktion mit Stannylenen

Hinz

Goicoechea

2016

Angewandte Chemie

View full text Add to dashboard Cite

[6][7][8][9] Metathesereaktionen çffnen den Zugang zu verschiedenen Koordinationsverbindungen von Hauptgruppenelementen, [10] Actinoiden [11] und Übergangsmetallen [12][13][14] sowie zu Phosphaketen-Verbindungen der Gruppe-14-und Gruppe-15-Elemente (Silyl bis Plumbyl, [15,16] Germylenyl [17][18][19] und Phosphanyl, [20][21][22][23] C). Darüber hinaus wurde auch über Cycloadditionen mit Alkinen, [24] Ketenen und Carbodiimiden berichtet. [25,26] Unter diesen vielen Studien finden sich nur drei Beispiele,indenen PCO À als Quelle von Phosphid (P À )dient:gegenüber Cyclotrisilenen (unter Bildung von D,A bbildung 1), [27] Imidazoliumsalzen [28] und Isocyanaten.[29]Die Chemie des schwereren Homologen AsCO À (des 2-Arsaethinolat-Ions) ist weniger gut entwickelt, da es erst 2016 als [Na(18-Krone-6)]AsCO isoliert werden konnte.[30] Es konnte gezeigt werden, dass AsCO À mit Heteroallenen als Quelle von As À dienen kann und dass es [2+ +2]-Cycloadditionen eingeht.Die Reaktivitätd er schweren Homologen des Cyanats gegenüber koordinativ ungesättigten Metallzentren ist bislang jedoch noch nicht untersucht. Wire ntschlossen uns daher,d iese Reaktivitätv on PCO À und AsCO À am Beispiel des von der Gruppe um Power entwickelten Bis(terphenyl)stannylens Te r 2 Sn (Ter = 2,6-Bis(2,4,6-trimethylphenyl)phenyl) zu untersuchen, da dieses durch die sterisch anspruchsvollen Te rphenyl-Substituenten als Monomer vorliegt. [31,32] Überraschenderweise gibt es nur wenige Studien zur Chemie dieses Stannylens (Schema 1), das sowohl mit Wasser und Alkoholen [33] als auch mit Alkyl-Aluminium-, Alkyl-Gallium- [34] und Alkyl-Zink-Verbindungen [35] reagiert, aber nicht mit weißem Phosphor. [36] Hier berichten wir über die Reaktivitätv on PCO À und AsCO À gegenüber Ter 2 Sn und demonstrieren die thermische oder photolytische Decarbonylierung von AsCO À ,d as dadurch als Quelle von As À gegenüber einer molekularen Spezies dient. Abbildung 1. Beispielef ürdie Reaktivitätvon PCO À (R = z. B. H, Cyclohexyl, Prop-2-in-1-yl). Dipp = 2,6-Diisopropylphenyl;T ipp = 2,4,6-Triisopropylphenyl.

show abstract

Convergent syntheses of [Sn7{C6H3-2,6-(C6H3-2,6-iPr2)2}2]: a cluster with a rare pentagonal bipyramidal motif

Abstract: Two complementary synthetic routes to a pentagonal bipyramidal Sn7 cluster, Sn7Aryl2 (Aryl = terphenyl ligand), are reported.

Cited by 79 publications

References 26 publications

Rationalizing and functionalizing stannaspherene: Very stable stannaspherene “alloys”

Rationalizing and functionalizing stannaspherene: Very stable stannaspherene “alloys”

Synthesis and characterization of novel eleven-vertex dimetallaheteroborane clusters containing Heavier group 16 elements

Eine monoanionische Arsenid‐Quelle: Decarbonylierung des 2‐Arsaethinolat‐Anions bei der Reaktion mit Stannylenen

Contact Info

Product

Resources

About