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. 2018 Feb 5;9(9):2601-2608.
doi: 10.1039/c8sc00190a. eCollection 2018 Mar 7.

Expansion of the (BB) 〉metallacycle with coinage metal cations: formation of B-M-Ru-B (M = Cu, Ag, Au) dimetalacyclodiboryls

Bennett J Eleazer  1 , Mark D Smith  1 , Alexey A Popov  2 , Dmitry V Peryshkov  1
Affiliations

Expansion of the (BB) 〉metallacycle with coinage metal cations: formation of B-M-Ru-B (M = Cu, Ag, Au) dimetalacyclodiboryls

Bennett J Eleazer et al. Chem Sci. .

Abstract

In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium-boron bonds on a surface of icosahedral boron clusters. M(i) cations (M = Cu, Ag, and Au) insert into B-Ru bonds of the (BB)-carboryne complex of ruthenium with the formation of four-membered B-M-Ru-B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B-M···Ru interactions that are isolobal to B-H···Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B-Au and Au-Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu-B (2.029(2) Å) and Ag-B (2.182(3) Å) bonds and the shortest Au-B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu(i) and Au(i) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M-B bonds.

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Figures

Scheme 1
Scheme 1. Coordination of coinage metal cations to strained B–Ru single bonds of the (BB)-carboryne complex with the formation of B–M–Ru–B metalacycles.
Fig. 1
Fig. 1. (a) Synthesis of [(POBBOP)(Ru)(CO)2(Cu)(Cl)]2 (2-Cu, POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane). (b, c) Displacement ellipsoid plot (50% probability) of the [(POBBOP)Ru(CO)2(Cu)(Cl)]2 complex (2-Cu). (b) A general view (c) a coordination environment of Ru and Cu centers. Note the distorted square-planar ligand arrangement around Cu(i). Atoms belonging to isopropyl groups of the ligand arms are omitted for clarity.
Fig. 2
Fig. 2. (a) Synthesis of [(POBBOP)Ru(CO)2(Au)(Cl)]2 (2-Au). (b, c) Displacement ellipsoid plot (50% probability) of the [(POBBOP)Ru(CO)2(Au)(Cl)]2 complex. (b) A general view (c) a coordination environment of Ru and Au centers. Note the distorted square-planar ligand arrangement around Au(i). Atoms belonging to isopropyl groups of the ligand arms are omitted for clarity.
Fig. 3
Fig. 3. (a) Synthesis of (POBBOP)(Ru)(CO)2(Ag)(CH3CN)(NO3) (2-Ag). (b, c) Displacement ellipsoid plot (50% probability) of the (POBBOP)(Ru)(CO)2(Ag)(CH3CN)(NO3) complex (2-Ag). (b) A general view (c) a coordination environment of Ru and Ag centers. Atoms belonging to isopropyl groups of the ligand arms are omitted for clarity.
Chart 1
Chart 1. Possible bonding descriptions of the coordination of coinage metal cations M+ to the (BB)Ru metalacycle.
Fig. 4
Fig. 4. (a–c) The contour map of electron density Laplacian and molecular graphs (based on the QTAIM bond paths) in the (B1–B2–Ru1–M) plane for 2-Cu, 2-Ag, and 2-Au (M = Cu, Ag, and Au; red curves denote electron density depletion, blue curves denote electron density concentration; blue dots are bond critical points). (d–f) ELF isosurfaces for selected valence basins for 2-Cu, 2-Ag, and 2-Au. V(B,B) (cyan), V(B,C) (pink), V(Ru,P)/V(Ru,C) (dark-blue) basins are shown at the level η = 0.8; V(Ru,B1), V(Ru,Cu,B2), V(Ru,Ag,B2), and V(Au,B) basins are shown at η = 0.7 in light green color; the V(Ru,Au) basin is shown in red at η = 0.4. Other basins are omitted for clarity.
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