Structural diversity for phosphine complexes of stibenium and stibinidenium cations

Chitnis, Saurabh S.; Peters, Brendan; Conrad, Eamonn; Burford, Neil; McDonald, Robert; Ferguson, Michael J.

doi:10.1039/c1cc15693d

Cited by 39 publications

(56 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Finally, it is notable that this is the only example coming from this study in which the phosphine has migrated from copper to the second metal center. Sb-P bonds are relatively common, and examples embracing simple R 3 P-Sb coordination include [{(Me 3 P)Ph 2 Sb} 4 X] 3+ [PF 6 ] 3 -(X = Cl, Br) (Wielandt et al, 2006), [(Me 3 P) 2 SbCl 2 ] + [CF 3 SO 3 ] - (Chitnis et al, 2011), [(Ph 3 P) 2 Ph 2 Sb] + [PF 6 ] - (Kilah et al, 2007) and (Me 3 P) 2 Sb 2 I 6 (Clegg et al, 1994a).…”

Section: Compound 8 Consists Of a Bimetallic [Sb 2 CL 9 Cu(pph 3 ) 2 mentioning

confidence: 99%

Synthesis and structures of Cu-Cl-M adducts (M=Zn, Sn, Sb)

Kociok‐Köhn

Mahon

Molloy

et al. 2014

Main Group Metal Chemistry

View full text Add to dashboard Cite

The novel bimetallic adducts [(Ph 3 P) 2 CuCl] 2 . have been synthesized from combinations of R 3 P, CuCl and one of ZnCl 2 , SnCl 2 or SbCl 3 , and their structures were determined. [(Me 3 P) 2 Cu] + [HPMe 3 ] 2 + [Sb 2 Cl 9 ] 3-(8) and [(Me 3 P) 4 Cu] + [(Me 3 P) 2 Sb 2 Cl 7 ] -(9) have been isolated as minor by-products from the reaction of Me 3 P, CuCl and SbCl 3 , and their structures were also determined.

show abstract

Section: Compound 8 Consists Of a Bimetallic [Sb 2 CL 9 Cu(pph 3 ) 2 mentioning

confidence: 99%

Synthesis and structures of Cu-Cl-M adducts (M=Zn, Sn, Sb)

Kociok‐Köhn

Mahon

Molloy

et al. 2014

Main Group Metal Chemistry

View full text Add to dashboard Cite

show abstract

“…Cationic frameworks exhibit an enhanced Lewis acidity compared with neutral analogues and recent reports of cationic complexes of p-block acceptors represent a new direction for coordination chemistry. [2,3] For example, complexes of mono-, [4] di-, [5] and tricationic [6] + , through sequential replacement of an anionic substituent (X) by neutral ligand(s) (L). Indeed, a number of cationic complexes containing tetrahedral P V acceptor centers have been structurally characterized, [7][8][9][10][11] although in all but a single case [7] ligand coordination is facilitated by a low coordination number at a phosphorus center involved in multiple bonding.…”

mentioning

confidence: 99%

Coordination Complexes of Ph₃Sb²⁺ and Ph₃Bi²⁺: Beyond Pnictonium Cations

et al. 2014

Self Cite

View full text Add to dashboard Cite

, through sequential replacement of an anionic substituent (X) by neutral ligand(s) (L). Indeed, a number of cationic complexes containing tetrahedral P V acceptor centers have been structurally characterized, [7][8][9][10][11] although in all but a single case [7] ligand coordination is facilitated by a low coordination number at a phosphorus center involved in multiple bonding.Here we report the synthesis and comprehensive characterization of complexes with the generic formula [Ph 3 PnL 2 ] 2+ for Pn = Sb or Bi, and L = OPPh 3 or 4-(dimethylamino)pyridine (dmap), which demonstrate a preference for axial coordination of the L donors. In addition, we report analogous complexes of Ph 3 Pn 2+ for Pn = Sb or Bi, with the chelating donor 2,2'-bipyridine (bipy). The results confirm the cations of general formula [R 3 PnL 2 ] 2+ (Pn = Sb or Bi) that were postulated on the basis of spectroscopic and conductivity measurements. [12,13]

show abstract

“…Consequently, many compounds of the heavy elements adopt coordination polymeric arrays in the solid state through intermolecular donor-acceptor interactions. (4)] increases the Lewis acidity of the acceptor, thus enabling a diversification of coordination chemistry, but examples are rare, [1,2] as are examples of heterolytic cleavage of a third EÀX bond [Eq. (1)].…”

mentioning

confidence: 99%

2,2‐Bipyridine Complexes of Antimony: Sequential Fluoride Ion Abstraction from SbF₃ by Exploiting the Fluoride Ion Affinity of Me₃Si⁺

2013

Self Cite

View full text Add to dashboard Cite

The coordination chemistry of the p-block elements as Lewis acceptors is superficially developed relative to that of the transition metals, despite the ability of the heavy p-block elements to access coordination numbers of six or greater. Consequently, many compounds of the heavy elements adopt coordination polymeric arrays in the solid state through intermolecular donor-acceptor interactions. Molecular complexes are known for many p-block element acceptors which are analogous to transition-metal complexes, with a neutral ligand (L) providing an additional bond to a neutral acceptor center (E; p-block element), even with retention of a lone pair at the acceptor site [Eq. (1)]. Alternatively, a neutral ligand can displace an anionic substituent (X; leaving group) to introduce a cationic charge on the complex, depending on the relative bond strengths of EÀX and EÀL, and the lattice energy of the resulting salt [Eq. (2)]. Such coordinative interactions are more generally applicable when the E À X bond is activated by an abstracting agent (A) [Eq. (3)]. The activation of a second E À X bond [Eq. (4)] increases the Lewis acidity of the acceptor, thus enabling a diversification of coordination chemistry, but examples are rare, [1,2] as are examples of heterolytic cleavage of a third EÀX bond [Eq. (5)]. [3][4][5] In an attempt to systematically and rationally augment the Lewis acidity of p-block elements and develop the coordination chemistry of p-block elements, we have examined a variety of reagent combinations of an element halide with a halide abstracting agent and a neutral ligand, and have discovered that mixtures of SbF 3 , Me 3 SiOSO 2 CF 3 (TMSOTf), and 2,2-bipyridine (bipy) in acetonitrile give compounds 1, 2, and 3 in high yield upon isolation depending on the applied stoichiometry (n and m; see Scheme 1). The substantial thermodynamic preference for the formation of Me 3 SiF (b.p. 16.5 8C) is evidenced by gaseous evolution and by the characteristic doublet in the 1 H NMR spectrum of the reaction mixture.Compounds 1, 2, and 3 were isolated and characterized using NMR spectroscopy and elemental analysis. All are extremely moisture sensitive and exposure of the solid results in protonation of the ligands within minutes. The X-ray structures of 1 and 3 are shown in Figures 1 a and b, respectively, and selected structural parameters are listed in Table 1. It has not yet been possible to determine the solidstate structure of compound 2. The solid-state structure of 1 is best described as a triflate salt of a difluorostibenium cation, [SbF 2 ] + , which is asymmetrically chelated at antimony by a bipy ligand. The antimony center also engages in weak interactions with one oxygen atom of the anion and a fluorine Scheme 1. Synthesis of compounds 1 (n = m = 1), 2 (n = m = 2), and 3 (n = 2, m = 3) by the stoichiometric abstraction of fluoride ions from SbF 3 by [Me 3 Si] + .

show abstract

Structural diversity for phosphine complexes of stibenium and stibinidenium cations

Cited by 39 publications

References 15 publications

Synthesis and structures of Cu-Cl-M adducts (M=Zn, Sn, Sb)

Synthesis and structures of Cu-Cl-M adducts (M=Zn, Sn, Sb)

Coordination Complexes of Ph₃Sb²⁺ and Ph₃Bi²⁺: Beyond Pnictonium Cations

2,2‐Bipyridine Complexes of Antimony: Sequential Fluoride Ion Abstraction from SbF₃ by Exploiting the Fluoride Ion Affinity of Me₃Si⁺

Contact Info

Product

Resources

About

Structural diversity for phosphine complexes of stibenium and stibinidenium cations

Cited by 39 publications

References 15 publications

Synthesis and structures of Cu-Cl-M adducts (M=Zn, Sn, Sb)

Synthesis and structures of Cu-Cl-M adducts (M=Zn, Sn, Sb)

Coordination Complexes of Ph3Sb2+ and Ph3Bi2+: Beyond Pnictonium Cations

2,2‐Bipyridine Complexes of Antimony: Sequential Fluoride Ion Abstraction from SbF3 by Exploiting the Fluoride Ion Affinity of Me3Si+

Contact Info

Product

Resources

About

Coordination Complexes of Ph₃Sb²⁺ and Ph₃Bi²⁺: Beyond Pnictonium Cations

2,2‐Bipyridine Complexes of Antimony: Sequential Fluoride Ion Abstraction from SbF₃ by Exploiting the Fluoride Ion Affinity of Me₃Si⁺