CONFORMATIONAL DIVERSITY IN THE SOLID-STATE STRUCTURES OF [RH-2(MU-CH3N(P(OCH3)(2))(2))(2)(CH3N(P(OCH3)(2))(2))(2)]X(2) (X=O3SCF3, B(C6H5)(4))
CONFORMATIONAL DIVERSITY IN THE SOLID-STATE STRUCTURES OF [RH-2(MU-CH3N(P(OCH3)(2))(2))(2)(CH3N(P(OCH3)(2))(2))(2)]X(2) (X=O3SCF3, B(C6H5)(4))
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DOI：
10.1016/0020-1693(94)04221-g
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发表时间：
1995-02-01
影响因子：
2.8
通讯作者：
MAGUE, JT
中科院分区：
文献类型：
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作者：
MAGUE, JT
[Rh-2(mu-CH3N(P(OCH3)(2))(2))(2)- (CH3N(P(OCH3)(2))(2))(2)]X(2) (X=O3SCF3 (1), B(C6H5), (2, 3a, 3b)) 中几个配体甲氧基的构象发生显着变化，导致 Rh-Rh 分离范围为1 中的 3.2727(5) 埃至 3b 中的双核阳离子中的 3.0821(39) 埃存在于三氟甲磺酸盐的固态结构 (1) 和四苯基硼酸盐的两种晶型变体 (2, 3) 中。这是由于晶体中阴离子的不同尺寸和堆积引起的离子间接触程度的变化。四苯硼酸盐中较松散的堆积也允许三重激发态的热激活构象变化。配合物 2: [Rh-2(mu-CH3N(P(OCH3)(2))(2))(2)(CH3N( P(OCH3)(2))(2))(2)](B(C6H5) 单斜晶系，P2(1)/n，a=13.899(3)，b=19.986(5)，c=28.089(8) 埃， beta=90.92(2)度，Z=4。配合物3：[Rh-2(mu-CH3N(P(OCH3)(2))(2))(2)(CH3N(P(OCH3)(2))(2))(2)](B(C6H5)(4))(2) 0.64CH(2)Cl(2)，单斜晶系，C2/c， a=65.943(12)，b=14.280(3)，c=27.055(6)埃，β=96.41(2)度，Z=12。
A significant variation in the conformation of several ligand methoxy groups in [Rh-2(mu-CH3N(P(OCH3)(2))(2))(2)- (CH3N(P(OCH3)(2))(2))(2)]X(2) (X=O3SCF3 (1), B(C6H5), (2, 3a, 3b)) which results in Rh-Rh separations ranging from 3.2727(5) Angstrom in 1 to 3.0821(39) Angstrom in 3b within the dinuclear cations is found in the solid state structures of the triflate salt (1) and two crystalline modifications of the tetraphenylborate salt (2, 3). This is attributed to variations in the extent of interionic contacts which arise from the different sizes and packing of the anions in the crystal. The looser packing in the tetraphenylborate salts also permits a thermally activated conformational change in the triplet excited state. Complex 2: [Rh-2(mu-CH3N(P(OCH3)(2))(2))(2)(CH3N( P(OCH3)(2))(2))(2)](B(C6H5) monoclinic, P2(1)/n, a=13.899(3), b=19.986(5), c=28.089(8) Angstrom, beta=90.92(2)degrees, Z=4. Complex 3: [Rh-2(mu-CH3N(P(OCH3)(2))(2))(2)(CH3N(P(OCH3)(2))(2))(2)](B(C6H5)(4))(2) . 0.64CH(2)Cl(2), monoclinic, C2/c, a=65.943(12), b=14.280(3), c=27.055(6) Angstrom, beta=96.41(2)degrees, Z=12.