Grocholl Luke, Huch Volker, Stahl Lothar, Staples Richard J., Steinhart Phaedra, Johnson Alison
Department of Chemistry, St. Cloud State University, St. Cloud, Minnesota 56301-4498.
Inorg Chem. 1997 Sep 24;36(20):4451-4457. doi: 10.1021/ic970287+.
The interaction of (MeSiN(t)Bu)(2)(N(t)BuLi)(2) with MCl(4) in hot toluene produces {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2,) M = Zr (1), Hf (2), in good yields. The light-yellow and colorless solids are isostructural and crystallize in the monoclinic crystal system, space group P2(1)/n, with four molecules in the unit cell. The unit cell dimensions for 1 (293 K) are a = 9.174(6) Å, b = 18.027(13) Å, c = 16.515 Å, beta = 98.81(6) degrees, and those for 2 (213 K) are a = 9.1871(1) Å, b = 17.8553(2) Å, c = 16.4770(3) Å, beta = 99.339(1) degrees. The metal atoms are pseudotetrahedrally coordinated by cyclodisilazane and chloride ligands but have one additional weak bonding interaction with a cyclodisilazane ring-nitrogen atom. Treatment of 1 or 2 with 2 equiv of MeMgCl in ether affords the corresponding dimethyl species {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2), M = Zr (3), Hf (4). These isostructural, colorless organometallic compounds are remarkably stable to atmospheric oxygen and moisture. They crystallize in the monoclinic space group C2/c, Z = 4. The cell parameters for 3 (298 K) are a = 18.867(2) Å, b = 9.361(1) Å, c = 18.059(3) Å, beta = 119.49(1) degrees, and those for 4 (212 K) are a = 18.8066(4) Å, b = 9.3208(2) Å, c = 17.8725(3) Å, beta = 119.508(1) degrees. The dimethyl species are structurally very similar to the dichloro complexes 1 and 2, with the notable exception that the metal centers in these organometallic compounds are truly four-coordinate.
(MeSiN(t)Bu)(2)(N(t)BuLi)(2) 与 MCl(4) 在热甲苯中反应，能以较高产率生成 {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2)，其中 M = Zr (1)、Hf (2)。浅黄色和无色固体为同构体，在单斜晶系中结晶，空间群为 P2(1)/n，晶胞中有四个分子。1（293 K）的晶胞参数为 a = 9.174(6) Å，b = 18.027(13) Å，c = 16.515 Å，β = 98.81(6)°；2（213 K）的晶胞参数为 a = 9.1871(1) Å，b = 17.8553(2) Å，c = 16.4770(3) Å，β = 99.339(1)°。金属原子由环二硅氮烷和氯配体伪四面体配位，但与一个环二硅氮烷环氮原子还有一个额外的弱键相互作用。在乙醚中用 2 当量的 MeMgCl 处理 1 或 2，可得到相应的二甲基化合物 {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2)，其中 M = Zr (3)、Hf (4)。这些同构的无色有机金属化合物对大气中的氧气和水分具有显著的稳定性。它们在单斜空间群 C2/c 中结晶，Z = 4。3（298 K）的晶胞参数为 a = 18.867(2) Å，b = 9.361(1) Å，c = 18.059(3) Å，β = 119.49(1)°；4（212 K）的晶胞参数为 a = 18.8066(4) Å，b = 9.3208(2) Å，c = 17.8725(3) Å，β = 119.508(1)°。二甲基化合物在结构上与二氯配合物 1 和 2 非常相似，值得注意的是，这些有机金属化合物中的金属中心是真正的四配位。
