Anion stabilised hypercloso-hexaalane Al6H6

被引：35

作者：

Bonyhady, Simon J. ^{[1
]}

Collis, David ^{[1
]}

Holzmann, Nicole ^{[2
]}

Edwards, Alison J. ^{[3
]}

Piltz, Ross O. ^{[3
]}

Frenking, Gernot ^{[4
]}

Stasch, Andreas ^{[1
,5
]}

Jones, Cameron ^{[1
]}

机构：

[1] Monash Univ, Sch Chem, POB 23, Clayton, Vic 3800, Australia

[2] STFC Rutherford Appleton Lab, Sci Comp Dept, Didcot OX11 0QX, Oxon, England

[3] Australian Nucl Sci & Technol Org, Australian Ctr Neutron Scattering, Locked Bag 2001, Kirrawee Dc, NSW 2232, Australia

[4] Philipps Univ Marburg, Fachbereich Chem, D-35032 Marburg, Germany

[5] Univ St Andrews, EaStCHEM Sch Chem, St Andrews KY16 9ST, Fife, Scotland

来源：

NATURE COMMUNICATIONS | 2018年 / 9卷

基金：

澳大利亚研究理事会;

关键词：

MAGNESIUM(I) DIMERS; HYDRIDE COMPLEXES; CLUSTER; ACTIVATION; ADDUCT; ANALOG; METAL;

D O I：

10.1038/s41467-018-05504-x

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Boron hydride clusters are an extremely diverse compound class, which are of enormous importance to many areas of chemistry. Despite this, stable aluminium hydride analogues of these species have remained staunchly elusive to synthetic chemists. Here, we report that reductions of an amidinato-aluminium(III) hydride complex with magnesium(I) dimers lead to unprecedented examples of stable aluminium(I) hydride complexes, [((Ar)Nacnac) Mg](2)[Al6H6(Fiso)(2)] ((Ar)Nacnac = [HC(MeCNAr)(2)](-), Ar = C6H2Me3-2,4,6 Mes; C6H3Et2-2,6 Dep or C6H3Me2-2,6 Xyl; Fiso = [HC(NDip)(2)](-), Dip = C(6)H(3)Pri(2)-2,6), which crystallographic and computational studies show to possess near neutral, octahedral hypercloso-hexaalane, Al6H6, cluster cores. The electronically delocalised skeletal bonding in these species is compared to that in the classical borane, [B6H6](2-). Thus, the chemistry of classical polyhedral boranes is extended to stable aluminium hydride clusters for the first time.

引用

页数：6

共 27 条

[11] Dimeric magnesium(I) β-diketiminates: a new class of quasi-universal reducing agent [J].

Jones, Cameron .

NATURE REVIEWS CHEMISTRY, 2017, 1 (08)

[12] Activation of CO by Hydrogenated Magnesium(I) Dimers: Sterically Controlled Formation of Ethenediolate and Cyclopropanetriolate Complexes [J].

Lalrempuia, Ralte ;

Kefalidis, Christos E. ;

Bonyhady, Simon J. ;

Schwarze, Benedikt ;

Maron, Laurent ;

Stasch, Andreas ;

Jones, Cameron .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (28) :8944-8947

[13] Unexpected stability of Al4H6:: A borane analog? [J].

Li, X. ;

Grubisic, A. ;

Stokes, S. T. ;

Cordes, J. ;

Gantefoer, G. F. ;

Bowen, K. H. ;

Kiran, B. ;

Willis, M. ;

Jena, P. ;

Burgert, R. ;

Schnoeckel, H. .

SCIENCE, 2007, 315 (5810) :356-358

[14] The hexagallane [Ga6{SiMe(SiMe3)2}6] and the closo-hexagallanate [Ga6{Si(CMe3)3}4 (CH2C6H5)2]2- -: the transition to an unusual precloso-cluster [J].

Linti, G ;

Çoban, S ;

Dutta, D .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2004, 630 (02) :319-323

[15] Structures and Stabilities of Small, Ligated AlnLn0/2- and AlnLn+2 Clusters (L = H, Cl) - A Theoretical Study [J].

Marchal, Remi ;

Manca, Gabriele ;

Kahlal, Samia ;

Carbonniere, Philippe ;

Pouchan, Claude ;

Halet, Jean-Francois ;

Saillard, Jean-Yves .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (30) :4856-4866

[16]

Martin D.R., 1959, J CHEM ED, V36, P208, DOI DOI 10.1021/ED036P208

[17] Ab initio study of the hypercloso boron hydrides BnHn and BnHn-.: Exceptional stability of neutral B13H13 [J].

McKee, ML ;

Wang, ZX ;

Schleyer, PV .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (19) :4781-4793

[18] hypercloso-Hexa(amino)hexaboranes: Structurally Related to Known hypercloso-Dodecaboranes, Metastable with Regard to Their Classical Cycloisomers [J].

Mesbah, Wahid ;

Soleimani, Meisam ;

Kianfar, Elham ;

Geiseler, Gertraud ;

Massa, Werner ;

Hofmann, Matthias ;

Berndt, Armin .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (36) :5577-5582

[19] POLYHEDRAL SKELETAL ELECTRON PAIR APPROACH [J].

MINGOS, DMP .

ACCOUNTS OF CHEMICAL RESEARCH, 1984, 17 (09) :311-319

[20]

N├a┬Ath H., 2004, MOL CLUSTERS MAIN GR, P34

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