Carboranyl C-σ-bonded and C-functionalized carboranes as ligands in gold and silver chemistry

Crespo, Olga; Gimeno, M. Concepción; Laguna, Antonio

doi:10.1016/j.jorganchem.2008.11.069

Cited by 23 publications

(10 citation statements)

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“…[23] 1,2-Dicarboranyl ligands and the potentially chelating 2,2'-bis(dicarboranyl) dianion are more electron-withdrawingt han aryl ligands. [24] However,i nc ontrast to the large number of dicarboranyl derivatives of Au I , [25][26][27][28][29][30][31] to the best of our knowledge there are no reports of dicarboranyl complexes of gold(III). [32] We therefore explored synthetic routes to Au III complexes with [C 2 B 10 H 11 ] À and [2,2'-(C 2 B 10 H 10 ) 2 ] 2À ligands and report here the synthesis and structures of the first examples of well-characterised gold(III) dicarboranyl derivatives.…”

Section: Introductionmentioning

confidence: 99%

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Chambrier

Hughes

Jeans

et al. 2020

Chemistry A European J

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The reaction of 1,1'-Li 2 [(2,2'-C 2 B 10 H 10 ) 2 ]w ith the cyclometallated gold(III) complex( C^N)AuCl 2 afforded the first examples of gold(III) dicarboranyl complexes. The reactivity of these complexes is subject to the trans-influence exerted by the dicarboranyl ligand,w hichi ss ubstantially weaker than that of non-carboranyl anionic C-ligands. In line with this, displacemento fc oordinated pyridine by chloride is only possible under forcing conditions. While treatment of (C^N)Au{(2,2'-C 2 B 10 H 10 ) 2 }( 2)w ith triflic acid leads to AuÀC rather than AuÀNb ond protonolysis, aqueous HBr cleaves the AuÀNb ond to give the pyridinium bromo complex 7.The trans-influence of as eries of ligands including dicarboranyl and bis(dicarboranyl) was assessed by meansofD FT calculations. The analysis demonstrated that it was not suffi-cient to rely exclusively on geometricd escriptors (calculated or experimental) when attempting to rank ligands fort heir trans influence. Complex( C^N)Au(C 2 B 10 H 11 ) 2 containing two non-chelating dicarboranyll igandsw as prepared similar to 2.I ts reaction with trifluoroacetic acida lso leads to AuÀN cleavage to give trans-(Hpy^C)Au(OAc F )(C 2 B 10 H 11 ) 2 (8). In crystals of 8 the pyridiniumN ÀHb ond points towards the metal centre, while in 7 it is bent away.T he possible contribution of gold(III)···HÀNh ydrogen bonding in these complexes was investigated by DFT calculations. The results show that, unlike the situation for platinum(II), there is no evidencef or an energeticallys ignificant contribution by hydrogen bonding in the case of gold(III).

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Section: Introductionmentioning

confidence: 99%

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Chambrier

Hughes

Jeans

et al. 2020

Chemistry A European J

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“…[18,19] In contrast to monocarba-closo-borates, the coordination chemistry of dicarba-closo-dodecaboranes and dicarbacloso-decaboranes with 2c-2e s bonds between one or both cluster carbon atoms and metal centers is well established. [20] Some linear gold(I) complexes with 1,2-1,7-, and 1,12-dicarba-closo-dodecaboranes with tertiary phosphane and arsane ligands have been reported [21] and synthetic, spectroscopic, and structural properties are available for most of these coordination compounds. [22][23][24][25][26][27][28][29] These complexes have unexpected thermal stability and are chemically inert.…”

Section: àmentioning

confidence: 99%

Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

Finze

Sprenger

2009

Chemistry A European J

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The anionic gold(I) complexes [1-(Ph(3)PAu)-closo-1-CB(11)H(11)](-) (1), [1-(Ph(3)PAu)-closo-1-CB(9)H(9)](-) (2), and [2-(Ph(3)PAu)-closo-2-CB(9)H(9)](-) (3) with gold-carbon 2c-2e sigma bonds have been prepared from [AuCl(PPh(3))] and the respective carba-closo-borate dianion. The anions have been isolated as their Cs(+) salts and the corresponding [Et(4)N](+) salts were obtained by salt metathesis reactions. The salt Cs-3 isomerizes in the solid state and in solution at elevated temperatures to Cs-2 with DeltaH(iso)=(-75+/-5) kJ mol(-1) (solid state) and DeltaH( not equal)=(118+/-10) kJ mol(-1) (solution). The compounds were characterized by vibrational and multi-NMR spectroscopies, mass spectrometry, elemental analysis, and differential scanning calorimetry. The crystal structures of [Et(4)N]-1, [Et(4)N]-2, and [Et(4)N]-3 were determined. The bonding parameters, NMR chemical shifts, and the isomerization enthalpy of Cs-3 to Cs-2 are compared to theoretical data.

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“…Monosubstitution of the carboranes is not trivial because the monolithiation of the o-carborane moiety is complicated by the tendency of the monolithio o-carborane to disproportionate into o-carborane and its dianion [14]. Several strategies Over the years, our group and others have been interested in the synthesis of new carborane-based ligands containing a variety of donor centers (N, P, S, N/C, N/S, N/P, P/C, P/P P/Si, P/S, S/C or S/S donors) and their metal complexes an applications [2,6,[18][19][20][21][22][23][24][25][26][27][28]. Carborane ligands containing N,O donors are scarce in the literature.…”

Section: Introductionmentioning

confidence: 99%

N,O-Type Carborane-Based Materials

2016

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This review summarizes the synthesis and coordination chemistry of a series of carboranyl ligands containing N,O donors. Such carborane-based ligands are scarcely reported in the literature when compared to other heteroatom-containing donors. The synthetic routes for metal complexes of these N,O-type carborane ligands are summarized and the properties of such complexes are described in detail. Particular attention is paid to the effect that the incorporation of carboranes has into the coordination chemistry of the otherwise carbon-based ligands and the properties of such materials. The reported complexes show a variety of properties such as those used in magnetic, chiroptical, nonlinear optical, catalytic and biomedical applications.

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Carboranyl C-σ-bonded and C-functionalized carboranes as ligands in gold and silver chemistry

Cited by 23 publications

References 69 publications

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

N,O-Type Carborane-Based Materials

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Carboranyl C-σ-bonded and C-functionalized carboranes as ligands in gold and silver chemistry

Cited by 23 publications

References 69 publications

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry

Anionic Gold(I) Complexes—Twelve‐ and Ten‐Vertex Monocarba‐closo‐borate Anions with Carbon–Gold σ Bonds

N,O-Type Carborane-Based Materials

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Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry

Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of Au^III Dicarboranyl Chemistry