Coordination of Ortho-Chlorines in Copper (I) and Silver (I) 2,6-Di- and 2,4,6-Trichlorophenolates

Abstract

The crystal structure of (Ph 3 P) 2 AgOC 6 H 2 Cl 3 (I) is reported along with the syntheses and 35 C1 and 63 Cu NQR spectra of I and several related silver (I) and copper (I) 2,6-di-and 2,4,6-trichlorophenolates containing phosphines, phosphites, and pyridine as co-ligands. I crystallizes in space group P2 Jc with a= 16.692(4) Ä, b= 17.942 (4) A, c= 12.857 (3) Ä, /? = 97.60 (1)°, F = 3816.68 Ä 3 , and Z = 4. The final R (F) = 0.0475 and R (W) = 0.0396. Ag is coordinated in a trigonal planar geometry by the P atoms of the two triphenylphosphine ligands and the O atom of the chlorophenolate; Ag is then capped by one ortho-chlorine of the trichlorophenolate ligand at a distance of 3.160 (2) Ä. In the 35 C1 NQR spectrum of this compound the two orf/io-chlorines of the trichlorophenolate ligand have a large frequency difference of 1.500 MHz, indicating that one ortho-chlorine is coordinated to the silver; 35 C1 NQR spectra of related complexes are also presented and discussed. The 35 C1 NQR frequency differences of coordinated and non-coordinated orr/io-chlorines in metal chlorophenolates correlate well with the metal-chlorine distances but not with the metal-chlorine-carbon bond angles. A different correlation is found for the silver complexes of dichloroalkanes; possible reasons for this are discussed.

Comparative structural studies on silver(i) complexes with tripodal polyphosphines. Crystallographic characterisation of the first infinite chain structures in 2 ∶ 1 adducts of silver(i) halides with 1,1,1-tris(diphenylphosphinomethyl)ethane

“…The crystallographic characterisation of complex 6 was done using crystals obtained by recrystallization of Ag(NP 3 )Cl in CH 2 Cl 2 /CH 3 CN. Crystals suitable for X-ray diffraction studies of Ag 2 (CP 3 )Cl 2 (8ؒ2DMF) and Ag 2 (CP 3 )Br 2 (9) were obtained from DMF solutions of Ag(CP 3 )ClؒEt 2 Oؒ CHCl 3 (1ؒEt 2 OؒCHCl 3 ) and Ag(CP 3 )Brؒ3H 2 O (2ؒ3H 2 O) respectively. However, the X-ray structure of complex Ag 2 (CP 3 )I 2 ؒ 3DMSO (10ؒ3DMSO) was determined using crystals grown (size: 0.34 × 0.17 × 0.07 mm) from DMSO solutions of Ag 2 (CP 3 )I 2 ؒ2H 2 O (10ؒ2H 2 O).…”

“…2 : 1 and 3 : 1 Complexes. The position and number of bands assigned in the far IR spectra to ν(Ag-X) for complexes Ag 2 (CP 3 )X 2 (8)(9)(10) indicate that X is coordinating to silver() in a bridging mode. 45 Because of the splitting of ν a (N-O) in the IR spectra of the nitrate derivatives, Ag 2 (PP 3 )(NO 3 ) 2 (11), Ag 2 (NP 3 )(NO 3 ) 2 (12), Ag 3 (PP 3 )(NO 3 ) 3 (13) and Ag 3 (NP 3 )-(NO 3 ) 3 (14), the structures seem to involve the participation of nitrate groups as coordinating ligands in accordance with structures proposed in solution.…”

“…The very short structural information obtained for halide complexes Ag 2 (CP 3 )X 2 (8)(9)(10) in solution found compensation in solid state with the formation of crystals suitable for X-ray crystallography studies.…”

“…The number of asymmetric units per chain along the propagation axis for 8 and 10 is two. However crystals of complex Ag 2 (CP 3 )Br 2 (9) are made up of infinite linear chains with the monomer units related solely by translation. There are now four chains running through the unit cell (Fig.…”

Dioxin Precursors: NQR Studies of Group 1 and Related 2,6-Dichlorophenolate and 2,4,6-Trichlorophenolate Salts

“…Silver(I) and copper(I) ions coordinate readily [9] to chlorophenolate orf/io-chlorines, producing large (1.5-2.0 MHz) 35 C1 NQR low-frequency shifts for those chlorines; it is by no means obvious whether these M-Cl interactions (secondary bonding) [10] are principally electrostatic or covalent. Since Cu + and Ag + are similar in size and charge to the smaller Group 1 cations, the results can be compared to determine whether electrostatic interactions alone could suffice to produce 2-MHz frequency shifts.…”