The Preparation and Characterisation of Hetero‐ and Homobimetallic Complexes Containing Bridging Naphthalene‐1,8‐dithiolato Ligands

“…Synthesis of binuclear iridium(II) complexes with variety of naphthalene dithiolate motifs[95].Scheme 60. Synthesis of naphthalene dithiolate bimetallic complexes from platinum complex 112a[108].…”

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Synthesis of ligands based on naphthalene peri-substituted by Group 15 and 16 elements and their coordination chemistry

Kilián

Knight

Woollins

2011

Coordination Chemistry Reviews

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“…The rigidity of the organic backbone and the geometric constraints unique to these compounds, imposed by a double substitution at the close peri -positions, ensures metal coordination is favoured in order to achieve a relaxed geometry [ 24 ]. We have previously utilised the naphthalene backbone to prepare a variety of chalcogen and phosphorus compounds and associated metal complexes [ 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 ]. Our current work has focussed on the acenaphthene backbone, preparing halogen-chalcogen and chalcogen-chalcogen derivatives [ 49 , 50 , 51 ] and a series of halogen-tin compounds [ 52 ].…”

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confidence: 99%

Investigating Silver Coordination to Mixed Chalcogen Ligands

et al. 2012

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Six silver(I) coordination complexes have been prepared and structurally characterised. Mixed chalcogen-donor acenaphthene ligands L1–L3 [Acenap(EPh)(E'Ph)] (Acenap = acenaphthene-5,6-diyl; E/E' = S, Se, Te) were independently treated with silver(I) salts (AgBF4/AgOTf). In order to keep the number of variables to a minimum, all reactions were carried out using a 1:1 ratio of Ag/L and run in dichloromethane. The nature of the donor atoms, the coordinating ability of the respective counter-anion and the type of solvent used in recrystallisation, all affect the structural architecture of the final silver(I) complex, generating monomeric, silver(I) complexes {[AgBF4(L)2] (1 L = L1; 2 L = L2; 3 L = L3), [AgOTf(L)3] (4 L = L1; 5 L = L3), [AgBF4(L)3] (2a L = L1; 3a L = L3)} and a 1D polymeric chain {[AgOTf(L3)]n 6}. The organic acenaphthene ligands L1-L3 adopt a number of ligation modes (bis-monodentate μ2-η2-bridging, quasi-chelating combining monodentate and η6-E(phenyl)-Ag(I) and classical monodentate coordination) with the central silver atom at the centre of a tetrahedral or trigonal planar coordination geometry in each case. The importance of weak interactions in the formation of metal-organic structures is also highlighted by the number of short non-covalent contacts present within each complex.

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“…[13] To supplement our initial platinum study, [NapS 2 Pt(PPh 3 ) 2 ] was further treated with a range of Pt, Pd, Rh, Ir and Mo complexes to afford a series of bimetallic complexes containing an MM`S 2 core. [14] The corresponding reactions with [AuPPh 3 ]ClO 4 and AgClO 4 afforded binuclear and tetranuclear gold clusters and tri-or tetranuclear silver clusters, the outcome dependent upon the stoichiometry of the reactants. [15] Further examples of multimetallic complexes bearing naphthalene dithiolate ligands have been reported in the literature, with examples of tetra-and pentanuclear copper(I) complexes of 1,8-naphthalene dithiolate [16] and oligmomeric, dimeric and monomeric zinc complexes of 2,7-di-tert-butylnaphtho [1,8-c,d] [1,2]dithiole and naphthoic anhydride dithiole.…”

Section: Introductionmentioning

confidence: 99%

Platinum Complexes of 5,6‐Dihydroacenaphtho[5,6‐cd]‐1,2‐dichalcogenoles

et al. 2012

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Six platinum bisphosphine complexes, bearing dichalcogen acenaphthene ligands, have been prepared by metathesis from cis-[PtCl 2 (PR 3 ) 2 ] (R 3 = Ph 3 , Ph 2 Me, PhMe 2 ) and the dilithium salts of the parent 5,6-dihydroacenaphtho[5,6-cd]-1,2-dichalcogenoles [AcenapE 2 ] (L1 E = S, L2 E = Se). For their synthesis, the appropriate disulfide or diselenide species was treated with super hydride [LiBEt 3 H] affording the dilithium salt by in situ reduction of the AcenapE 2 E-E bond. Further reaction, via metathetical addition to the cis-platinum precursor afforded the respective platinum(II) complex [Pt(5,6-AcenapE 2 )(PR 3 ) 2 ] (R 3 = Ph 3 : E = S 1, Se 2; R 3 = Ph 2 Me: E = S 3, Se 4; R 3 = PhMe 2 : E = S 5, Se 6).All six complexes have been fully characterised, principally by multinuclear magnetic resonance spectroscopy, IR and MS. Selenium complexes 4 and 6 provide examples of AA`X spin systems, as displayed by their 31 P{ 1 H} NMR spectra. X-ray structures were determined for L1, L2, 1, 2, 5 and 6 and analysed, where appropriate, by platinum metal geometry, periatom displacement, splay angle magnitude, acenaphthene ring torsion angles and E···E interactions. Platinum was found to adopt a distorted square-planar geometry in all four complexes, with the nature of the AcenapE 2 ligand playing little part in the conformation of the substituents bound to the trivalent phosphorus atoms.____________ [a] EASTChem, School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK. Fax: (+44)1334 463384 E-mail: jdw3@st-and.ac.uk Supporting information for this article is available on the WWW under http://www.eurjic.org/ or from the author. IntroductionThe coordination chemistry of peri-substituted naphthalenes and structurally related systems has been developed over the last 15 years. [1] Geometric constraints unique to these frameworks are imposed by a double substitution at the peri-positions (positions 1 and 8 of the naphthalene ring, 5 and 6 of acenaphthene), [2,3] placing large heteroatoms or groups in close proximity, usually within van der Waals radii.[4] A number of investigators have utilised this characteristic of the naphthalene scaffold to study bonding interactions in main group systems, where molecular geometry is determined by a competition between attractive (covalent and weak) forces and repulsive interactions (steric strain). [5,6] The distinguishing feature of peri-substitution is the ability to achieve a relaxed geometry via formation of a direct bond between the two peri-atoms. [7] Furthermore, proximity effects associated with peri-substitution favours complexation to a bridging metal species, providing the correct spacial arrangement for bidentate coordination.Transition metal complexes incorporating 1,8-disubstituted naphthalene ligands have been well documented, [1] with the majority of examples reported bearing either bis(phosphine) or bis(thiolate) functionalities. Complexes assembled from ligands with Group 16 donor atoms invariably contain the naphthalene-1,8-dichalcogenol...

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The Preparation and Characterisation of Hetero‐ and Homobimetallic Complexes Containing Bridging Naphthalene‐1,8‐dithiolato Ligands

Cited by 26 publications

References 54 publications

Synthesis of ligands based on naphthalene peri-substituted by Group 15 and 16 elements and their coordination chemistry

Synthesis of ligands based on naphthalene peri-substituted by Group 15 and 16 elements and their coordination chemistry

Investigating Silver Coordination to Mixed Chalcogen Ligands

Platinum Complexes of 5,6‐Dihydroacenaphtho[5,6‐cd]‐1,2‐dichalcogenoles

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