Palladium complexes containing novel cyclic selenium imides

Risto, Maarit; Eironen, Aino; Männistö, Elisa; Oilunkaniemi, Raija; Laitinen, Risto S.; Chivers, Tristram

doi:10.1039/b910049k

Cited by 13 publications

(24 citation statements)

References 17 publications

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“…shown by 125 Te NMR to adopt a butterfly structure with exo Te atoms. 80 A number of studies have reported the oxidation of P(III) to P(V) by a range of chalcogen sources; reaction of RPCl 2 (R = Me, Et, i Pr, t Bu, Ph, Ad, 2-thiophenyl) with M 2 Se and M 2 Se 2 (2 : 2 : 1) afforded [(RP) 2 Se 4 ]M 2 (M = Li, Na).…”

Section: àmentioning

confidence: 99%

Oxygen, sulfur, selenium, tellurium and polonium

Clark

Melen

Rawson

2010

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Section: àmentioning

confidence: 99%

Oxygen, sulfur, selenium, tellurium and polonium

Clark

Melen

Rawson

2010

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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“…7 Cyclic selenium imides; Se4(N t Bu)3 (17) is only known as a ligand in a metal complex (Section 3.6). 41 This journal is © The Royal Society of Chemistry 20xx…”

Section: Figmentioning

confidence: 99%

“…46 The seven-membered ring Se4(N t Bu)3 (17) depicted in Fig. 5 has not been isolated in the reaction of SeCl2 with t BuNH2, however it has been identified in the palladium complex [PdCl217], which is formed in small amounts, together with [PdCl219] from the reaction of t BuN=Se=N t Bu with PdCl2(NCPh)2 in THF for 16 h. 41 In a separate experiment it was shown by 77 Se NMR spectroscopy that the six-membered ring Se3(N t Bu)3 (13) is transformed into the corresponding cyclic tetramer Se4(N t Bu)4 (19) in the presence of [PdCl2(NCPh)2], suggesting that ring transformations of the cyclic selenium imides may be promoted in the presence of a metal centre. 41 The seven-membered Se4(N t Bu)3 ring in [PdCl217] is Se,Sechelated to palladium via the selenium atoms that have two nitrogen neighbours, while the bidentate coordination mode for the eight-membered Se4(N t Bu)4 ring in [PdCl219] involves two antipodal selenium atoms (Fig.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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Insights into the formation of inorganic heterocycles via cyclocondensation of primary amines with group 15 and 16 halides

Chivers

Laitinen

2017

Dalton Trans.

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Cyclocondensation is a major preparative route for the generation of inorganic heterocycles especially in the case of ring systems involving a Group 15 or 16 element linked to nitrogen. This Perspective will consider recent experimental and computational studies involving the reactions of primary amines (or their synthetic equivalents) with pnictogen and chalcogen halides. The major focus will be a discussion of the identity and role of acyclic intermediates in the reaction pathways to ring formation, as well as the nature of the heterocycles so formed. The similarities and differences between the chemistry of group 15 and 16 systems are emphasised with a view to providing signposts for further investigations.

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“…The molecular structure of the complex in (35), (tris(t-butylimido)tetraselane)-dichlorido-palladium benzonitrile solv- ate [53], features a buckled, seven-membered [SeNSe 2 NSeN] ring with two selenium(II) atoms coordinated to a palladium atom. One of the non-coordinating selenium(II) atoms forms a Se(lp)···π(arene) interaction with the benzonitrile ring [d = 3.57 Å and θ = 14.4°] (Figure 14.17c).…”

Section: Selenium(ii)mentioning

confidence: 99%

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

Tiekink¹,

Zukerman-Schpector²

2017

Multi-Component Crystals

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Since the disclosure of tellurium(II, IV)···π(aryl) interactions in their crystal structures [1], there has been increasing interest in ascertaining the importance of this type of supramolecular synthon, i.e. main group element(lp)···π(arene), in the structural chemistry of main group element chemistry [2][3][4][5][6][7][8][9][10]. It is noted in passing that analogous interactions have been revealed in structural biology and are known to provide important stabilising contacts [11,12]. In molecular structural chemistry, the emphasis thus far has been upon seeking "stand-alone" element(lp)···π(arene) contacts and determining the supramolecular architectures they sustain [2][3][4][5][6][7][8][9][10]. Usually these architectures are zero-and one-dimensional; however, examples of two-and even three-dimensional aggregation patterns are known [9,10]. With the restriction that the element(lp)···π(arene) interaction operates in a given dimension within a crystal, in isolation from other supramolecular synthons, these interactions occur in a maximum of 14% of thallium(I) structures. This is reduced to 9% in bismuth(III) structures and down to a minimum of 2-3% for tin(II) and lead(II) compounds [9,10]. In terms of bonding, it is likely that the lone-pair···π interaction has similar features to halogen bonding [13] in that there is an asymmetric distribution of electron density in the lone-pair of electrons. This leaves an electropositive region at the tip of the lone-pair that interacts with the π electrons of the ring. This electron-deficient region is termed variously a σ-hole or polar cap, and the energy of stabilisation imparted by these interactions is in the region of 10 kJ mol −1 , i.e. similar to that imparted by C-H···π(aryl) interactions. In keeping with the theme of the present volume, "Aspects of Multi-Component Crystals: Synthesis, Concepts and Function", a description herein of the supramolecular architectures sustained by main group element(lp)···π(aryl) interactions is given where the π system is a solvent molecule such as benzene. ProceduresStandard protocols were utilised to identify structures for the current survey [10]. The Cambridge Structural Database (CSD: version 5.37 + 2 updates) [14] was searched using CONQUEST (version 1.18) [15]. There were two key geometric restraints, as illustrated in Figure 14.1a. The first restraint is the distance d, between the metal centre and the ring centroid, labelled Cg, which was set at 4.0 Å. This distance is shown to be suffihttps://doi

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Palladium complexes containing novel cyclic selenium imides

Abstract: The first metal complexes of cyclic selenium(II) imide ligands, [PdCl2{Se,Se'-Se4(NtBu)3}] and [PdCl2{Se,Se'-Se4(NtBu)4}], which are obtained from the reaction of Se(NtBu)2 with [PdCl2(NCPh)2], contain the novel Se-N heterocycles Se4(NtBu)3 and Se4(NtBu)4.

Cited by 13 publications

References 17 publications

Oxygen, sulfur, selenium, tellurium and polonium

Oxygen, sulfur, selenium, tellurium and polonium

Insights into the formation of inorganic heterocycles via cyclocondensation of primary amines with group 15 and 16 halides

14. Solute–solvent interactions mediated by main group element(lone-pair)···π(aryl) interactions

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