cyanide in dichloromethane leads to the isolation of polycyanide oligomers such as [C(12)N(12)](2)(-) and [C(4)N(4)](-), which was crystallographically characterized as the PPN(+) salt C(40)H(30)N(5)P(2): monoclinic space group = I2/a, a = 18.6314(2) A, b = 9.1926(1) A, c = 20.8006(1), beta =106.176(2) degrees, Z = 4]. In the solid state Mn(IV)-CN bond homolysis is thermally activated above 122 degrees C
第一种已知的顺磁性四面体
氰化物络合物[Mn(II)(CN)(4)](2)(-)是通过[Mn(IV)(CN)(6)](2)的光致分解形成的(-)在非
水溶液中或通过固态热分解。在
乙腈或
二氯甲烷中,光激发进入
配体到
金属的电荷转移带(lambda(max)= 25 700 cm(-1),epsilon = 3700 cm(-1)M(-1))会导致
氰化物的均质裂解自由基和Mn(IV)的还原。
二氯甲烷中的游离
氰化物导致分离出多
氰化物低聚物,例如[C(12)N(12)](2)(-)和[C(4)N(4)](-),其结晶学特征为P
PN(+)盐C(40)H(30)N(5)P(2):单斜空间群= I2 / a,a = 18.6314(2)A,b = 9.1926(1)A,c = 20.8006( 1),β= 106.176(2)度,Z = 4]。在固态下,根据差示扫描量热法测量,Mn(IV)-CN键均质分解在1