Syntheses and cadmium-113 NMR studies of five-coordinate complexes with CdN{sub 5}, CdN{sub 3}O{sub 2}, and CdN{sub 3}S{sub 2} central cores. Solid state structures of [HB(3-Phpz){sub 3}]Cd[H{sub 2}B(3,5-Me{sub 2}pz){sub 2}] and [HB(3,5-Me{sub 2}pz){sub 3}]Cd[S{sub 2}CNEt{sub 2}] (pz = Pyrazolyl)
- Univ. of South Carolina, Columbia, SC (United States); and others
The reaction of CdCl{sub 2} with equimolar amounts of K[HB(3,5-Me{sub 2}pz){sub 3}] (pz = pyrazolyl) and K[H{sub 2}B(3,5-Me{sub 2}pz){sub 2}] or K[HB(3-Phpz){sub 3}] and either K[H{sub 2}B(pz){sub 2}] or K[H{sub 2}B(3,5-Me{sub 2}pz){sub 2}] yields, respectively, the five-coordinate complexes [HB(3,5-Me{sub 2}pz){sub 3}]Cd[H{sub 2}B(3,5-Me{sub 2}pz){sub 2}] (1), [HB(3-Phpz){sub 3}]Cd[H{sub 2}B(pz){sub 2}] (2) and [HB(3-Phpz){sub 3}]Cd[H{sub 2}B(3,5-Me{sub 2}pz){sub 2}] (3). The structure of 3 has been characterized in the solid state by X-ray crystallography. The complex has a square pyramidal arrangement of the nitrogen donor atoms about cadmium. Solution state {sup 1}H NMR studies indicate that this geometry is retained in solution. Complexes 1-3 show solution {sup 113}Cd NMR resonances in the range {delta} 193.6-224.3 ppm (vs Cd(Cl0{sub 4}){sub 2}). The complexes containing the [HB(3-Phpz){sub 3}]{sup -} ligand have the more shielded resonances. This range overlaps the region observed for poly(pyrazolyl)borate complexes with CdN{sub 6} inner cores ({delta} 94.0-221.1 ppm). Six complexes with a CdN{sub 3}O{sub 2} inner core of the formula [HB(3-Phpz){sub 3}]Cd[(RCO){sub 2}CH] (R = Bu{sup t}, Ph, CF{sub 3}), [HB(3-Bu{sup t}pz){sub 3}]Cd[(Bu{sup t}CO){sub 2}CH], [B(3-Pr{sup i}pz){sub 4}]Cd(Bu{sup t}CO){sub 2}CH], and [HB(3-Bu{sup t}pz){sub 3}Cd(CH{sub 3}CO{sub 2}) have been prepared by the reaction of CdCl{sub 2} or Cd(NO{sub 3}){sub 2} and the appropriate ligand salts. Two complexes with N{sub 3}S{sub 2} inner cores, [HB(3,5-Me{sub 2}pz){sub 3}]Cd[Et{sub 2}NCS{sub 2}] (10) and [HB(3-Phpz){sub 3}]Cd[Et{sub 2}NCS{sub 2}] (11), have been prepared. The structure of 10 has been determined by X-ray crystallography. The donor atoms are arranged about cadmium in an irregular five-coordinate geometry.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 191950
- Journal Information:
- Inorganic Chemistry, Vol. 34, Issue 20; Other Information: PBD: 27 Sep 1995
- Country of Publication:
- United States
- Language:
- English
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