Syntheses and Solid State Structures of Tris(pyrazolyl)methane Complexes of Sodium, Potassium, Calcium, and Strontium: Comparison of Structures with Analogous Complexes of Lead(II)
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- 作者：Daniel L. Reger ; Christine A. Little ; Mark D. Smith ; Arnold L. Rheingold ; Louise M. Liable-Sands ; Glen P. A. Yap ; and Ilia A. Guzei
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：January 14, 2002
- 年：2002
- 卷：41
- 期：1
- 页码：19 - 27
- 全文大小：133K
- 年卷期：v.41,no.1(January 14, 2002)
- ISSN：1520-510X
文摘
The reaction of NaI with 2 equiv of HC(pz)3 or HC(3,5-Me2pz)3 (pz = pyrazolyl ring) leads to the formation of{[HC(pz)3]2Na}(I) (1) and {[HC(3,5-Me2pz)3]2Na}(I) (2), respectively. Both compounds have trigonally distortedoctahedral arrangements about the sodium. A similar reaction of KPF6 with HC(3,5-Me2pz)3 results in the formationof {[HC(3,5-Me2pz)3]2K}(PF6) (3), a complex also shown crystallographically to have a trigonally distorted octahedralarrangement about the potassium, which is an unusually low coordination number for this large metal ion. Thecomplex {[HC(pz)3]2Sr}(BF4)2 (4) forms in the reaction of Sr(acac)2 (acac = acetylacetonate) with HBF4·Et2Ofollowed by 2 equiv of HC(pz)3. The structure is highly distorted, showing 
3 bonding of both tris(pyrazolyl)methaneligands and, in addition, interactions with the metal from three fluorine atoms from the BF4- counterions. Thesymmetrical structure of 1 and the nine-coordinate structure of 4 are both very different from the distorted, six-coordinate structure {[HC(pz)3]2Pb}(BF4)2, indicating that for this compound the lone pair on lead(II) is influencingthe structure. The reaction of M(acac)2 (M = Sr, Ca) with H{B[3,5-(CF3)2C6H3]4} followed by 2 equiv of HC(pz)3produces {[HC(pz)3]2(Hacac)Sr}{B[3,5-(CF3)2C6H3]4}2 (5) (when the reaction is done in CH2Cl2), {[HC(pz)3]2(Me2CO)2Sr}{B[3,5-(CF3)2C6H3]4}2 (6) (when the reaction is done in acetone), and {[HC(pz)3]2(Hacac)Ca}{B[3,5-(CF3)2C6H3]4}2 (7), respectively. The structures of all three complexes show a distorted eight-coordinate arrangementof the ligands about the metal. Crystal data: 1 is orthorhombic, Pnma, a = 16.931(1), b = 22.368(3), c = 7.937(2) Å, 
= 90, 
= 90, 
= 90
, Z = 4; 2 is trigonal, R
, a = 10.7483(8), b = 10.7483(8), c = 35.395(4) Å, = 90, = 90, = 120, Z = 3; 3 is monoclinic, P21/c, a = 9.144(4), b = 13.377(6), c = 15.988(7) Å, =90, = 92.291(10), = 90, Z = 2; 4 is hexagonal, P65, a = 9.42530(10), b = 9.42530(10), c = 55.3713(5)Å, = 90, = 90, = 120, Z = 6; 5 is monoclinic, P2/n, a = 14.1601(3), b = 13.1756(3), c = 27.1826(6)Å, = 90, = 90.1744(7), = 90, Z = 2; 6 is monoclinic, P2/n, a = 14.2709(7), b = 13.2646(7), c =27.4189(13) Å, = 90, = 90.3850(10), = 90, Z = 2; 7 is monoclinic, P2/n, a = 14.2388(2), b = 13.1919(2), c = 26.7879(3) Å, = 90, = 90.0650(8), = 90, Z = 2.
3 bonding of both tris(pyrazolyl)methaneligands and, in addition, interactions with the metal from three fluorine atoms from the BF4- counterions. Thesymmetrical structure of 1 and the nine-coordinate structure of 4 are both very different from the distorted, six-coordinate structure {[HC(pz)3]2Pb}(BF4)2, indicating that for this compound the lone pair on lead(II) is influencingthe structure. The reaction of M(acac)2 (M = Sr, Ca) with H{B[3,5-(CF3)2C6H3]4} followed by 2 equiv of HC(pz)3produces {[HC(pz)3]2(Hacac)Sr}{B[3,5-(CF3)2C6H3]4}2 (5) (when the reaction is done in CH2Cl2), {[HC(pz)3]2(Me2CO)2Sr}{B[3,5-(CF3)2C6H3]4}2 (6) (when the reaction is done in acetone), and {[HC(pz)3]2(Hacac)Ca}{B[3,5-(CF3)2C6H3]4}2 (7), respectively. The structures of all three complexes show a distorted eight-coordinate arrangementof the ligands about the metal. Crystal data: 1 is orthorhombic, Pnma, a = 16.931(1), b = 22.368(3), c = 7.937(2) Å, = 90, = 90, = 90, Z = 4; 2 is trigonal, R, a = 10.7483(8), b = 10.7483(8), c = 35.395(4) Å, = 90, = 90, = 120, Z = 3; 3 is monoclinic, P21/c, a = 9.144(4), b = 13.377(6), c = 15.988(7) Å, =90, = 92.291(10), = 90, Z = 2; 4 is hexagonal, P65, a = 9.42530(10), b = 9.42530(10), c = 55.3713(5)Å, = 90, = 90, = 120, Z = 6; 5 is monoclinic, P2/n, a = 14.1601(3), b = 13.1756(3), c = 27.1826(6)Å, = 90, = 90.1744(7), = 90, Z = 2; 6 is monoclinic, P2/n, a = 14.2709(7), b = 13.2646(7), c =27.4189(13) Å, = 90, = 90.3850(10), = 90, Z = 2; 7 is monoclinic, P2/n, a = 14.2388(2), b = 13.1919(2), c = 26.7879(3) Å, = 90, = 90.0650(8), = 90, Z = 2.