Coordination chemistry of halocarbons

Preparation and characterization of Tl(1,2-C2H4Cl2)B(OTeF5)4: a metal complex of a least coordinating solvent and a least coordinating anion

“…' Based on IR and NMR spectroscopic data, others have concluded that dichloromethane can coordinate to Mo and W (15) or to Re (1 6), respectively. Many examples of M -C l ( C ) linkages have been reported in compounds in which the chlorine atom is a substituent on a much stronger ligand such as an amine or a phenoxide ( 17). ( 1 ) c (1) 1390 ( 15) 4370 (12) 2825 (14) 50 (6) C(2) 2920 ( 15) 4882 (11) 3659 ( 14) 5 l(7) B 4024 ( 14) 1681 (10) 7903 (10) 20 (4) Te (1) 3102 (1) -931 (1) 5888 (1) 20 (1) o ( 1 ) 4246 (8) 737 (6) 6815 (6) 27(3) F (1) 2280 (8) (6) 6950 (6) 43(3) F (4) 1414 (7) -760 (5) 6438 (5) 29(2) F (5) 2006 (7) -2580 (5) 4879 (5) 33(3) Te (2) 2524 (1) 3399 (1) 7025 ( 1) 23 (1) O (2) 2721 (8) 2 190 (6) 7650 (6) 26(3) F (6) 1171 (8) 21 63 (7) 5645 (6) 45(3) F (7) 958 (8) 37 1...…”

The Coordination Chemistry of the CF Group of Fluorocarbons: Thermodynamic Data and Ab Initio Calculations on CF-Metal Ion Interactions

“…[1] The first systematic investigations of fluorocarbon ± metal coordination were performed in the early 1980s by Glusker, Murray-Rust et al, who found unusually short CF ± metal ion contacts in some X-ray crystal structures. [2] In the following years further complexes displaying these features, mainly with the hard metal ions of Groups 1 and 2, were structurally characterized, [3,4] but as late as the early 1990s evidence for such interactions in solution remained scarce. [5] This changed when Plenio et al synthesized partially fluorinated crown ethers and cryptands, which allowed the first systematic studies of CF ± metal ion coordination.…”

Coordination of Ortho-Chlorines in Copper (I) and Silver (I) 2,6-Di- and 2,4,6-Trichlorophenolates

“…But in the theory for secondary-bridging halogen atoms (in which the bond to the metal atom is much weaker) it is assumed that it is energetically unfavorable to hybridize the halogen just to form a very weak bond to a metal. Consequently the NQR frequency should have no dependence on the C-Cl-M bond angle, and this bond angle should be in the vicinity of 90°, as is observed empirically [14] and has been predicted from theoretical calculations [35]. Thus the NQR data suggest that, despite the closeness of approach of the chlorine and metal in some of these compounds, the bond remains secondary, and thus distinct in nature from the carbon-chlorine bond.…”