Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre IV
Although some nickel complexes with P,N- or P,N,P-type ligands are diamagnetic in
solution, 60 complexes 17, 18, 20, 22 and 23 proved to be paramagnetic in CDCl3, CD2Cl2,
CD3CN, CD3CD2OD or CD3OD solution. Their magnetic moments per Ni atom, determined
by the Evans method in CD2Cl2, 61-64 were 2.2 (17), 2.7 (18), 2.8 (20), 3.0 (22) and 1.9 (23) µB
respectively. 65,66 These values are similar to those recently reported for other Ni(II)
complexes with P,N-type ligands. 34,47-50
These complexes have also been characterized by IR, elemental analysis and mass
spectrometry. High Resolution Mass Spectrometry (HRMS) with the ElectroSpray Ionisation
method afforded spectra where the main peak corresponds to [Ni(P,N)Cl] + . The structures of
18 and 22 are shown in Figures 2 and 3 and selected bond distances and angles are given in
Tables 1 and 2.
Table 1. Selected Bond Lengths (Å) and Angles (deg) in 18
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Ni-P 2.305(1) C6-C7 1.543(5)
Ni-N 2.061(3) C5-C6 1.500(5)
Ni-Cl1 2.291(1) C5-N 1.357(4)
Ni-Cl2 2.4227(9) P-C8 1.821(4)
Ni-Cl3 2.3508(9) P-C14 1.818(4)
P-C7 1.822(4)
Cl1-Ni-Nl2 158.69(4) Cl3-Ni-N 162.92(9)
Cl1-Ni-Cl3 92.09(4) Cl3-Ni-P 100.18(3)
Cl1-Ni-N 87.97(8) N-Ni-P 96.18(9)
Cl1-Ni-P 106.28(4) Ni-P-C7 105.5(1)
Cl2-Ni-Cl3 84.53(3) C7-C6-C5 113.4(3)
Cl2-Ni-N 89.23(8) C6-C5-N 118.5(3)
Cl2-Ni-P 95.03(3) C5-N-Ni 126.8(3)
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