The Choice of Coordination Number in d10 Complexes of Group 11 Metals

The Choice of Coordination Number in d10 Complexes of Group 11 Metals

The Choice of Coordination Number in d10 Complexes of Group 11 Metals

M Angels Carvajal, Juan J Novoa and Santiago Alvarez

Supporting Information

Structural Database Survey

The structural data used for Figure 1 were obtained through a systematic search for complexes of group 11 metals classified in the Cambridge Structural Database1 (CSD, version 5.23) as di-, tri- and tetracoordinate Only those structures that could be unambiguously identified as corresponding to oxidation state +1 were retained and structures presenting disorder or with agreement factors R in excess of 10 % were ruled out In the context of this work, the coordination number of a metal atom in a given crystal structure is the one that has been proposed by the authors of the crystallographic determination from a comparison of metal-ligand bond distances with the sum of atomic radii, as reflected in the CSD A breakdown of structures found in the CSD by metal and coordination number is presented in Table S1 In some cases (less than a 5% of the selected compounds) the assignment of coordination number to the metal atom is not straightforward, and the corresponding structures have been classified by us as “ambiguous” For instance, we assign an ambiguous coordination number two to those structures with bond angles of less than 140° Among

"tricoordinate" complexes, we count as having an ambiguous coordination number those in which the metal atom is at least 0.6 Å above (or below) the plane formed by the three donor atoms Finally, ambiguous tetracoordinate structures are considered to be those with one bond angle smaller than 60° or with torsion angles between two L-M-L groups smaller than 45° For statistical purposes (as reflected in Figure 1), however, we have kept the coordination number assigned by the CSD, given the small proportion of ambiguous cases.

All (ambiguous) "dicoordinate" molecules with bond angles smaller than 147° are seen to have metal-ligand contacts at less than 2.8 Å (13 crystallographically independent molecules in 9 compounds), mostly to sulfur or oxygen atoms, but also in one case6 to carbon atoms of a phenyl ring at 2.53, 2.91 and 2.96 Å, suggestive of a p-allylic coordination In all the ambiguous tricoordinate complexes the metal atom presents either one additional short contact

to a donor atom, indicating effective tetracoordination, or one too long "bond distance" that should be considered nonbonding, indicating an effective coordination number of two Similarly, the ambiguous tetracoordinate complexes have either one long metal-ligand bond distance and bond angles consistent with tricoordination, or two long bond distances and a nearly linear arrangement of the other two ligands, indicative of effective dicoordination

Table S1. Distribution of d10 complexes of group 11 metals with different coordination numbers (CN) in the Cambridge Structural Database (version 5.23) Both the number of independent crystallographic data sets (molecules) and of crystal structure determinations (structures) are given Criteria for number of fragments with ambiguous coordination number are discussed in the computational section, but the corresponding structures are counted with the coordination number assigned in the CSD.

M CN molecules structures ambiguous

Table S2 Basis sets employed for the DFT calculations.

a Huzinaga, S.; Andzelm, J.; Klobukowski, M.; Radzi-Andzelm, E.; Sakai, Y.; Tatewaki, H Gaussian

b Cu: Liu, X.-Y.; Mota, F.; Alemany, P.; Novoa, J J.; Alvarez, S Chem Commun 1998, 1149 Ag and

Au: dividing by 10 the smallest exponent of the LanL2DZ basis set

Table S3 Interaction and formation energies (Eint and Ef) calculated for the family of reactions[CuL1L2] + L3 with and without (in parentheses) counterpoise correction for the basis set superpositionerror.

Table S4. Optimized bond distances (Å) for dicoordinate d10 [MAB] complexes and ranges ofexperimental values found in the CSD.

Table S5. Calculated bond distances (Å) and anglesg for tricoordinate d10 [MAB2] complexes andranges of experimental values found in the Cambridge Structural Database (in parentheses).

Table S6. Calculated bond distances (Å) and angles for tetracoordinate d10 [MA4], complexes andranges of experimental values found in the Cambridge Structural Database N and Z are the number ofcrystal structure determinations and the number of crystallographically independent molecules fromwhich the corresponding experimental values were taken, respectively Calculated data correspond togeometries with frozen tetrahedral bond angles except where otherwise specified.

in [ML2X2] complexes; f) in [ML2X2] complexes.

Table S7. Calculated bond distances (Å) and angles for tetracoordinate d10 [MAB3], complexes andranges of experimental values found in the Cambridge Structural Database N and Z are the number ofcrystal structure determinations and the number of crystallographically independent molecules fromwhich the corresponding experimental values were taken, respectively Calculated data correspond togeometries with frozen tetrahedral bond angles except where otherwise specified.

in [ML2X2] complexes; f) in [ML2X2] complexes.

Table S8. Calculated bond distances (Å) and angles for tetracoordinate d10 [MA2B2], complexes andranges of experimental values found in the Cambridge Structural Database N and Z are the number ofcrystal structure determinations and the number of crystallographically independent molecules fromwhich the corresponding experimental values were taken, respectively Calculated data correspond togeometries with frozen tetrahedral bond angles except where otherwise specified.

in [ML2X2] complexes; f) in [ML2X2] complexes.

Table S9 Optimized geometries for [MCl(EMe3)2] complexes, compared to those of the unsubstituted [MCl(EH3)2] analogues (M = Cu, Ag or Au; E = N or P).

Table S10. Formation energies of tricoordinate complexes calculated in the gas phase and considering

a dielectric environment (CPCM approach) with bond angles frozen at 120° Values given inparentheses correspond to optimized geometries (Table 2)

X Ef (gas phase) Ef (water) Ef (CH2Cl2)[Cu(NH3)2]+ + NH3 -16.0 -5.4 -8.7

(-39.1) (-6.8) (-15.4)

(-33.0) (-5.9) (-12.8)

Table S11. Calculated bending and stretching energies (kcal/mol) for the [MAB] complexes at fixed bond angles of 120° in a tricoordinate complex Of the two values of Estr given, the first one corresponds to bond length relaxation after bending, the second one to the same degree of bond stretching prior to bending.

Table S12. Calculated pyramidalization energy for [MABC] trigonal complexes to tetrahedral angles (Epyr) and stretching energies for the relaxation of bond distances of the [MABC] fragment in tetrahedral complexes (Estr, first value corresponds to the maximum value in compounds resulting from the addtion of a neutral ligand, the value in parenthesis for compounds resulting from addition of a halide) All values in kcal/mol.

Table S13. Optimized metal-ligand bond distances in homoleptic [MLn]+ complexes as a function ofthe coordination number (Å).

Table S14. Ranges of calculated and experimental metal-ligand bond distances in [MABn-1]complexes (n = 2 – 4).

Figure S1. Distribution of L-Ag-L bond angles in AgI complexes described in the CSD as dicoordinate.

Figure S2. (a) Experimental Cu-X distances in [CuX(PR3)2] complexes (X = Br, empty squares and I, empty triangles) as a function of the P-Cu-P bond angle, and (b) Au-X distances

in [AuX(PR3)2] complexes (X = Cl, empty circles; Br, empty squares, and I, empty triangles) The corresponding calculated distances (Table 4) are shown as closed symbols.

Figure S3 Experimental Au-Cl distances in [AuXL3] complexes as a function of the sum of the L-Au-L bond angles.

Figure S4 Experimental Cu-X distances in [CuX(NR3)2] complexes as a function of the sum

of the N-Au-N bond angle.