Reaction of equimolar quantities of MX (M = Au, Cu, X = Cl; M = Ag, X = OTf) and GaCl(3) in CH(2)Cl(2) with P(4) leads to phosphorus ligating a cationic coinage metal centre. For Cu and Ag, ion-contacted coordination polymers are formed; for Au, an ion-separated complex is observed that features the [Au(η(2)-P(4))(2)](+) cation, which is the first homoleptic Au-P(4) complex to be characterised in the condensed phase.
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Probing the Structure, Dynamics and Bonding of Coinage Metal
Complexes of White PhosphorusLaura C. Forfar, [a] Dihao Zeng, [b] Michael Green, [a] John E. McGrady* [b] and Christopher A. Russell*
Lead halide perovskite nanocrystals have emerged as promising materials for optoelectronic ap-plications. Their properties can be tuned by changing the synthesis conditions, but usually theseconditions are studied in isolation rather...
A range of thio- and seleno-phosphonium cationic complexes [RE(PR'3)](+)[X](-) (R = Me, Ph; E = S, Se; X = GaCl4, SbF6) have been synthesised and structurally characterised. Reaction of [PhSPPh3][GaCl4] and [PhSePPh3][GaCl4] with P(t)Bu3 results in the ready transfer of the "RS(+)" and "RSe(+)" fragments from PPh3 to the stronger electron donor P(t)Bu3. NMR experiments combined with an Eyring analysis on the corresponding degenerate phosphine exchange reaction allowed the thermodynamic values for the phosphine exchange reaction of the sulfur cation (ΔH(‡) 18.7 ± 12.0 kJ mol(-1); ΔS(‡) -99.3 ± 36.3 J mol(-1) K(-1)) to be compared with the corresponding values (ΔH(‡) 2.4 ± 1.1 kJ mol(-1) and ΔS(‡) -58.1 ± 5.0 J mol(-1) K(-1)) for the [PhSePPh3](+) system. Importantly, the large negative entropy of activation and linear dependence on the rate of exchange are compatible with an SN2-type exchange process. This conclusion is supported by DFT calculations which confirm that the phosphine exchange process occurs via an associative mechanism. The rate of exchange was found to increase from sulfur to selenium and those with aryl substituents underwent exchange faster than those with alkyl substituents.
White Phosphorus as a Ligand for the Coinage Metals. -Copper and silver form coordination complexes with P4 whereas gold forms a homoleptic [Au(P4)2] + cation. The structures of (IV), (VI), and (VIII) are determined by single crystal XRD. (IV) crystallizes in the orthorhombic space group Ccca with Z = 2 and consists of chains of CuGaCl4 units linked by P4 molecules. (VI) and (VIII) crystallize in the orthorhombic space group Pnma with Z = 4. (VI) contains AgGaCl 4 ladders with η 2 -P 4 molecules bound to each Ag center. (VIII) displays ion-separated complexes in the solid state with the Au cation binding to two distorted tetrahedral P4 molecules in η 2 -fashion. -(FORFAR, L. C.; CLARK, T. J.; GREEN*, M.; MANSELL, S. M.; RUSSELL, C. A.; SANGURAMATH, R. A.; SLATTERY, J. M.; Chem. Commun. (Cambridge) 48 (2012) 14, 1970-1972, http://dx.doi.org/10.1039/c2cc15291f ; Sch. Chem., Univ. Bristol, Cantock's Close, Bristol BS8 1TS, UK; Eng.) -W. Pewestorf 18-013
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