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Theoretical calculations carried out at the B3PW91/6-311++G(d, p)//B3PW91 6-31 G(d) level of theory have demonstrated that both conformation of Xantphos-phosphole 1 have nearly the same energy (ΔE = +2.9 kcal/mol) at the same energy. In the first conformation the two phosphorus atom lone pair point towards the plane of symmetry of the ligand (to form, a chelate ligand) whereas in the second conformation (+2.9 kcal/mol) one phosphorus atom lone pair points outside the ligand explaining why a monodentate is formed when [Au-Cl] is reacted. The two conformations are in equilibrium through the inversion of one phosphorus atom of one phosphole ring. DFT calculations indicate that the inversion barrier in this type of 1,2,5-tris aryl substituted phosphole is about 16 kcal/ mol (RB3PW 6-311++G(d,p) level of theory).
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One reviewer of this article suggested that complex 3 could be obtained in pure form by submitting complex 4 to a metathesis with chloride salts. Several attempts were thus made using LiCl as salt in different solvents but each attempt resulted in the formation of 2 and 3 as a mixture.
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Despite many attempts, we could not avoid the presence of one very small imaginary frequency at -9.7650 corresponding mainly to the rotation of a phenyl group on one phosphole part of the ligand.
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