2,4,8,10-Tetra-tert-butyl-6-phenyldibenzo[d,g]-[1,3,6,2]dioxaselena-phos phocine Complexes: C-Se Bond Cleavage and Its Oxidative Addition to Form a Novel Octahedral Rhodium(III) Complex and Hirshfeld Analysis

Selenaphosphocine [(-OC6H2(tBu)(2)(mu-Se)(tBu)(2)C6H2O-)PhP] (1) on treatment with [Pd(COD)Cl-2] yielded P,Se-coordinated complex [{(-OC6H2(tBu)(2)(mu-Se)(tBu)(2)C6H2O-)PhP}(PdCl2)] (2), whereas the reaction of 1 with [AuCl center dot SMe2] resulted in only P-coordinated complex [{(-OC6H2(tBu)(2)(mu-Se)(tBu)(2)C6H2O-)PhP}(AuCl)] (4). The reaction of 1 with [Rh(CO)(2)Cl](2) in 4:1 molar ratio yielded a rare RhIII octahedral complex [{PhP(-OC6H2(tBu)(2)(mu-Se)(tBu)(2)C6H2O-)}{PPh(-OC6H2(tBu)(2))(Se(tBu)v(2)C(6)H(2)O-)}(RhCl)] (3) in good yield, in which one of the C-Se bonds of selenophosphocine is added oxidatively to RhI. All of the complexes have been structurally characterized and are crystallized in the triclinic crystal system with P(-)1 space group. All complexes showed intermolecular C-H center dot center dot center dot O and C-H center dot center dot center dot Se hydrogen bonding interactions, that play major role in the crystal packing to form a three-dimensional array. In complex 2, the crystal packing reveals the presence of rare intermolecular Pd center dot center dot center dot Cl interactions. Hirshfeld surface analysis, dnorm and two-dimensional fingerprint plots were investigated to validate the contributions of the different intermolecular contacts within the supramolecular structure. A Hirshfeld surface analysis indicated that the most significant contributions to the crystal packing of 2 are from H center dot center dot center dot H (66.3%), C center dot center dot center dot H/H center dot center dot center dot C (13.5%), Cl center dot center dot center dot H/H center dot center dot center dot Cl (13.7%), Cl center dot center dot center dot C/C center dot center dot center dot Cl (1.8%) and Cl center dot center dot center dot C/C center dot center dot center dot Cl (1.0%) contacts, and those for 3 are from HH (88.3%), C center dot center dot center dot H/H center dot center dot center dot C (8.3%) and Se center dot center dot center dot H/H center dot center dot center dot Se (3.6%) contacts, while those for 4 are from H center dot center dot center dot H (71.5%), C center dot center dot center dot H/H center dot center dot center dot C (9.9%), Cl center dot center dot center dot H/H center dot center dot center dot Cl (10.2%), Se center dot center dot center dot H/H center dot center dot center dot Se (2.7%) and Au center dot center dot center dot H/H center dot center dot center dot Au (1.7%) contacts. [GRAPHICS] .