Synthesis and coordination chemistry of 2,2′-diboratabiphenyls

2006 ◽  
Vol 84 (2) ◽  
pp. 81-92 ◽  
Author(s):  
Ioan Ghesner ◽  
Warren E Piers ◽  
Masood Parvez ◽  
Robert McDonald

Dianionic 2,2′-diboratabiphenyl derivatives were prepared as a new class of binucleating ligands. Preliminary investigations into their coordination chemistry involved Rh complexes. Their solution and solid state structures were studied and confirm the preference for η6–η6 coordination of the novel ligands, rendering them isoelectronic analogues of the ubiquitous bicyclopentadienyl system. Comparative studies suggest stronger donor properties for the fulvalene ligand as compared with the 2,2′-diboratabiphenyl system.Key words: dinucleating ligands, bimetallic complexes, rhodium complexes, boron heterocycles, X-ray structure.

Inorganics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 52
Author(s):  
Maximilian Dehmel ◽  
Helmar Görls ◽  
Robert Kretschmer

Dianionic N,N-chelating ligands play a crucial role in coordination chemistry, but reports on related complexes remain limited to certain types of ligands. In here, the reactions of two diprotic ligands, i.e., a biguanide and a carbothiamide, with trimethylaluminium, are reported, which give rise to mono- and dinuclear aluminium(III) complexes. In addition, single deprotonation of the diprotic biguanide using potassium bis(trimethylsilyl)amide gives rise to a one-dimensional coordination polymer. All complexes have been fully characterized, and their solid-state structures were determined by single crystal X-ray diffraction analysis.


1989 ◽  
Vol 42 (1) ◽  
pp. 149 ◽  
Author(s):  
LM Engelhardt ◽  
S Gotsis ◽  
PC Healy ◽  
JD Kildea ◽  
BW Skelton ◽  
...  

A number of 1 : 1 silver(1) halide/nitrogen base adducts, [ LAgX ], have been synthesized by recrystallization of the parent silver(I) halide from the neat base, and their solid state structures determined by single-crystal X-ray diffraction and rationalized in terms of the hierarchy of structural types described in the preceding papers based on steric profile of the base. In consequence of increased metal atom size (cf. Cu), a more limited array of structural types is observed.[(pyridine) AgBr,I ] ∞, [(2,4,6-trimethylpyridine) AgCI,Br,I ] ∞ and [( quinaldine ) AgCI,Br ] are 'stair' polymers; [( piperidine ) AgBr,I ]4 and [(2,2,6,6-tetramethyIpiperidine) AgI ]4 are 'cube' tetramers, while [( diethylamine ) AgCI,Br,I ] provide the first complete metal halide series of the novel 'tube' polymer.


Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 981
Author(s):  
Mason D. Hart ◽  
John J. Meyers ◽  
Zachary A. Wood ◽  
Toshinori Nakakita ◽  
Jason C. Applegate ◽  
...  

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)5Cr(2-isocyano-1,3-X2-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime “workhorse” aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr–CNAz bond distances}, cyclic voltametric {E1/2(Cr0/1+)}, 13C NMR {δ(13CN), δ(13CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {νN≡C, νC≡O, kC≡O} analyses of the [(OC)5Cr(2-isocyano-1,3-X2-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(13COtrans) vs. δ(13CN), δ(13COcis) vs. δ(13CN), and δ(13COtrans) vs. kC≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC6F5 and CNC2F3.


2007 ◽  
Vol 62 (10) ◽  
pp. 1339-1342 ◽  
Author(s):  
Surajit Jana ◽  
Tania Pape ◽  
Norbert W. Mitzel

The reaction of dimethylcadmium with alcohols R-OH in equimolar ratio leads to the formation of tetrameric methylcadmium alkoxides with molecular formula [(MeCd)4 (OR)4] [R = Me (1), Et (2) and iPr (3)]. These compounds have been characterised by 1H, 13C NMR and IR spectroscopy, by mass spectrometry, elemental analyses and by X-ray crystallography (for 2 and 3). The solid state structures show distorted cubane-type aggregates with Cd4O4 cores. The structural aspects and the spectroscopic characterisations of these compounds are discussed.


2016 ◽  
Vol 52 (66) ◽  
pp. 10144-10146 ◽  
Author(s):  
Felix Hanke ◽  
Sarah Hindley ◽  
Anthony C. Jones ◽  
Alexander Steiner

X-ray structures and DFT calculations show that the HT phase is of Me2Cd is two-dimensionally disordered, while the LT phase is ordered. Both phases contain linearly coordinated cadmium atoms; methyl groups are staggered in the HT form and eclipsed in the LT-form.


Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5745
Author(s):  
Sergey A. Anufriev ◽  
Sergey V. Timofeev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
Igor B. Sivaev

Complexation of the 8,8′-bis(methylsulfanyl) derivatives of cobalt and iron bis(dicarbollides) [8,8′-(MeS)2-3,3′-M(1,2-C2B9H10)2]− (M = Co, Fe) with copper, silver, palladium and rhodium leads to the formation of the corresponding chelate complexes, which is accompanied by a transition from the transoid to the cisoid conformation of the bis(dicarbollide) complex. This transition is reversible and can be used in design of coordination-driven molecular switches based on transition metal bis(dicarbollide) complexes. The solid-state structures of {(Ph3P)ClPd[8,8′- (MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} and {(COD)Rh[8,8′-(MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} were determined by single crystal X-ray diffraction.


2019 ◽  
Vol 48 (11) ◽  
pp. 3551-3554 ◽  
Author(s):  
Antonio J. Martínez-Martínez ◽  
Andrew S. Weller

We report an alternative, improved, multigram scale (∼20 g, 60–70% yield) preparation of solvent-free anhydrous Li[BArF4], Na[BArF4] and K[BArF4], and the corresponding single-crystal X-ray characterisation of [Li(H2O)][BArF4], Na[BArF4]˙ and K[BArF4].


2003 ◽  
Vol 58 (8) ◽  
pp. 809-812 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Oleg L. Tok ◽  
Amin Badshah

The crystal structure of tetra(propyn-1-yl)silane, Si(C≡CMe)4 1, has revealed a completely asymmetric molecule (point group C1). Since this finding concerns a single crystal, the bulk material of 1 was studied by solid-state 29Si and 13C MAS NMR. This confirmed the result of the X-ray analysis, and by comparison with previous NMR measurements of the tin analogue 1(Sn) it is concluded that 1 and 1(Sn) must have very similar solid-state structures which are in contrast to those known for other tetra(alkyn-1-yl)silicon and -tin compounds. The NMR data set of 1 in solution was completed by determination of the magnitude of coupling constants 1J(13C,13C).


2013 ◽  
Vol 66 (11) ◽  
pp. 1447 ◽  
Author(s):  
James E. M. Lewis ◽  
James D. Crowley

A series of copper(ii) complexes of the ligand 2,6-bis(pyridin-3-ylethynyl)pyridine have been synthesised and characterised by 1H and DOSY NMR, IR and UV-Vis spectroscopies, mass spectrometry, elemental analysis and single crystal X-ray diffraction. In solution these systems display almost identical spectroscopic properties, however the solid state structures are shown to vary widely, depending upon the choice of anion. The tetrafluoroborate salt was revealed to be a discrete Cu2L4 cage-like helicate. The tosylate salt, whilst of the same Cu2L4 stoichiometry, was shown to be a coordination polymer. Finally the nitrate salt structure was observed to be a discrete Cu2L2 metallocycle.


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