| Abstrakt: |
Selenaphosphocine [(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)PhP] (1) on treatment with [Pd(COD)Cl2] yielded P,Se-coordinated complex [{(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)PhP}(PdCl2)] (2), whereas the reaction of 1 with [AuCl⋅SMe2] resulted in only P-coordinated complex [{(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)PhP}(AuCl)] (4). The reaction of 1 with [Rh(CO)2Cl]2 in 4:1 molar ratio yielded a rare RhIII octahedral complex [{PhP(–OC6H2(tBu)2(µ-Se)(tBu)2C6H2O–)}{PPh(–OC6H2(tBu)2)(Se(tBu)2C6H2O–)}(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⋯O and C–H ⋯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⋯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⋯H (66.3%), C⋯H/H⋯C (13.5%), Cl⋯H/H⋯Cl (13.7%), Cl⋯C/C⋯Cl (1.8%) and Cl⋯C/C⋯Cl (1.0%) contacts, and those for 3 are from H⋯H (88.3%), C⋯H/H⋯C (8.3%) and Se⋯H/H⋯Se (3.6%) contacts, while those for 4 are from H⋯H (71.5%), C⋯H/H⋯C (9.9%), Cl⋯H/H⋯Cl (10.2%), Se⋯H/H⋯Se (2.7%) and Au⋯H/H⋯Au (1.7%) contacts. This paper describes the cleavage of a C–Se from dioxaselenaphosphocine and its oxidative addition to rhodium(I) complex and Hirshfeld analysis. [ABSTRACT FROM AUTHOR] |
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