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. 2024 Mar 5;29(5):1150.
doi: 10.3390/molecules29051150.

Welcoming Neighbour or Inhospitable Host? Selective Second Metal Binding in 5- and 6-Phospha-Substituted Bpy Ligands

James A Platts  1 , Benson M Kariuki  1 , Paul D Newman  1
Affiliations

Welcoming Neighbour or Inhospitable Host? Selective Second Metal Binding in 5- and 6-Phospha-Substituted Bpy Ligands

James A Platts et al. Molecules. .

Abstract

The controlled formation of mixed-metal bimetallics was realised through use of a fac-[Re(CO)3(N,N'-bpy-P)Cl] complex bearing an exogenous 2,4,6-trioxa-1,3,5,7-tetramethyl-8-phosphaadamantane donor at the 5-position of the bpy. The introduction of gold, silver, and rhodium with appropriate secondary ligands was readily achieved from established starting materials. Restricted rotation about the C(bpy)-P bond was observed in several of the bimetallic complexes and correlated with the relative steric bulk of the second metal moiety. Related chemistry with the 6-substituted derivative proved more limited in scope with only the bimetallic Re/Au complex being isolated.

Keywords: heterobimetallic complexes; phospha–bpy ligands; rotamers.

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Scheme 1
Scheme 1
Synthesis of the ligands CgP-5bpy (5L) and CgP-6bpy (6L).
Figure 1
Figure 1
Optimised geometry of 5LRe (hydrogens omitted for clarity). Light blue = Re; dark blue = N; green = Cl; red = O; orange = P.
Figure 2
Figure 2
Ortep [45] representation of the molecular structure of 5LRe,Au. Hydrogen atoms and residual solvent have been omitted for clarity. Selected bond lengths (Å) and angles (°): Re1—N1 2.170(5); Re1—N2 2.162(4); Re1—C21 1.925(6); Re1—C22 1.973(6); Re1—C23 1.924(6); Re1—Cl1 2.4483(16); Au1—P1 2.2177(14); Au1—Cl2 2.2786(15); N1—Re1—C23 170.1(2); N2—Re1—C21 171.9(2); Cl1—Re1—C22 176.42(17); P1—Au1—Cl2 179.34(7).
Figure 3
Figure 3
Geometry optimised molecular structure of 6LRe,Au. Light blue = Re; dark blue = N; green = Cl; red = O; orange = P; yellow = Au.
Figure 4
Figure 4
Ortep [45] representation of the molecular structure of anti-5LRe,Rh. Hydrogen atoms and residual solvent have been omitted for clarity. Selected bond lengths (Å) and angles (°): Re1—N1 2.173(3); Re1—N2 2.172(3); Re1—C11 1.902(6); Re1—C12 1.910(4); Re1—C13 1.908(5); Re1—Cl1 2.4563(18); Rh1—P1 2.3176(8); Rh1—Cl2 2.3580(8); N1—Re1—C13 171.67(14); N2—Re1—C12 173.15(15); Cl1—Re1—C11 179.1(2); P1—Rh1—Cl2 84.48(3).
Figure 5
Figure 5
Frontier orbitals of 5LRe,Au. (a) The HOMO (−6.09 eV); (b) the LUMO (−2.66 eV).
See this image and copyright information in PMC

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