Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
Supplementary
Bis[hydrotris(pyrazolyl)borato]manganese(II), [HB(pz)3]2Mn (1). The preparation of this
complex is described in the text.
Bis[tetrakis(pyrazolyl)borato]manganese(II), [B(pz)4]2Mn (2). Eighty milliliters of 0.05 M
sodium hydroxide containing K[B(pz)4] (1.909 g, 6.0 mmol) was added to 1 M hydrochloric acid (10
mL) containing MnCl2·4H2O (0.594 g, 3.0 mmol). Sodium hydroxide (1 M) was added and mixed
until a white precipitate no longer formed (pH 4.0). After 20 min, the precipitate was filtered off and
washed with distilled water and methanol. Crystals for the analytical sample and the X-ray structure
were obtained by recrystallization from dichloromethane. Anal. Calcd for C24H24N16B2Mn: C, 47.02;
H, 3.95; N, 36.55. Found: C, 46.98; H, 3.89; N, 36.79.
Bis[tetrakis(pyrazolyl)borato]cobalt(II), [B(pz)4]2Co (3). Eighty milliliters of 0.05 M sodium
hydroxide containing K[B(pz)4] (1.909 g, 6.0 mmol) was added to 1 M hydrochloric acid (20 mL)
containing CoCl2·6H2O (0.714 g, 3.0 mmol). Sodium hydroxide (1 M) was added and mixed until a
yellow precipitate no longer formed (pH 1.0). After 20 min, the precipitate was filtered off and washed
with distilled water and methanol. Crystals for the analytical sample and the X-ray structure were
obtained by recrystallization from chloroform. Anal. Calcd for C24H24N16B2Co: C, 46.71; H, 3.92; N,
36.32. Found: C, 46.37; H, 3.97; N, 36.31.
Bis[tetrakis(pyrazolyl)borato]nickel(II), [B(pz)4]2Ni (4). Eighty milliliters of 0.05 M sodium
hydroxide containing K[B(pz)4] (3.18 g, 10.0 mmol) was added to 1 M hydrochloric acid (20 mL)
containing Ni(NO3)2·6H2O (1.454 g, 5.0 mmol). Sodium hydroxide (1 M) was added and mixed until a
lilac precipitate no longer formed (pH 0.8). After 20 min, the precipitate was filtered off and washed
with distilled water and methanol. Crystals for the analytical sample and the X-ray structure were
obtained by recrystallization from chloroform. Anal. Calcd for C24H24N16B2Ni: C, 46.73; H, 3.92; N,
36.33. Found: C, 45.61; H, 3.89; N, 36.33.
Bis[tetrakis(pyrazolyl)borato]copper(II), [B(pz)4]2Cu (5). Eighty milliliters of 0.05 M sodium
hydroxide containing K[B(pz)4] (3.18 g, 10.0 mmol) was added to 1 M hydrochloric acid (20 mL)
containing CuCl2·2H2O (0.852 g, 5.0 mmol). Sodium hydroxide (1 M) was added and mixed until a
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Supplementary Material (ESI) for Dalton Transactions
This journal is © The Royal Society of Chemistry 2001
blue precipitate no longer formed (pH 1.0). After 20 min, the precipitate was filtered off and washed
with distilled water and methanol. Crystals for the analytical sample and the X-ray structure were
obtained by recrystallization from diethyl ether. Anal. Calcd for C24H24N16B2Cu: C, 46.36; H, 3.89; N,
36.05. Found: C, 46.14; H, 3.88; N, 36.08.
Bis[tetrakis(pyrazolyl)borato]zinc(II), [B(pz)4]2Zn (6). Eighty milliliters of 0.05 M sodium
hydroxide containing K[B(pz)4] (1.591 g, 5.0 mmol) was added to 1 M hydrochloric acid (20 mL)
containing ZnSO4·7H2O (0.719 g, 2.5 mmol). Sodium hydroxide (1 M) was added and mixed until a
white precipitate no longer formed (pH 2.0). After 20 min, the precipitate was filtered off and washed
with distilled water and methanol. Crystals for the analytical sample and the X-ray structure were
obtained by recrystallization from chloroform. Anal. Calcd for C24H24N16B2Zn: C, 46.23; H, 3.88; N,
35.94. Found: C, 46.25; H, 3.92; N, 36.49. 1H NMR (CDCl3, δ): 6.25 (br, 8H, 4-H(pz)), 7.38, 7.73 (br,
d, 8H, 8H, J = 2.2 Hz, 3-H, 5-H (pz)).
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