羰基金屬簇衍生物計有,[{Ru3(CO)11}2(trans-bdpe)](1),[Os3(
CO)10(dppf)](2),[Os3(CO)8(CL)3(cis-bdpe)](3),[Os3(XO)7(Ph)(CH3C(
CH2PPh2)(CH2PPh)(CH2PC6H4)](4).(1)和(2)以 TMNO 為起始劑在攝氏零
度下以化學氧化法製得. (3)和(4)以熱裂法製得.錯合物經紅外線光譜,元
素分析與 P-核磁共振光譜鑑定,並以X射線單晶繞射獲得其結構解析.
紅色晶體(1)為三斜晶系,空間群為P1, a=10.340(2), b=12.223(2),
c=12.743(3)最後 Rf=0.023(4813個繞射點). 分子為雙單元單取代結構,
有一個反置中心存在於碳碳雙鍵中間. 紅色晶體(2)為直方晶系,空間群
為Pbcn, a=16.179(2), b=16.850(3), c=18.247(3)最後 Rf=0.028(4368
個繞射點). 分子具有橋型環,且有一個二轉軸通過鐵原子及鋨原子. 紅
色晶體(3)為單斜晶系,空間群為P21, a=12.686(4), b=14.681(3),
c=15.683(3)最後 Rf=0.066(5022個繞射點). 分子內具有一個五員鉗合環
和一個六員橋型環. 紅色晶體(4)為單斜晶系,空間群為P21/C,
a=9.692(4), b=21.477(4), c=25.361(7)最後 Rf=0.104(5807個繞射點).
分子內有一個磷原子配位於軸向位置而另二個於赤道面位置,一獨立苯環
佔據赤道面位置而另一苯環以鄰位配位於金屬.

The derivaties of the Metal carbonyl cluster, [{Ru3(CO)11}2(
trans-bdpe)](1), [Os3(CO)10(dppf)](2),[Os3(CO)8(CL)3(cis-bdpe)
](3),[Os3(CO)7(Ph)(CH3C(CH2PPh2)(CH2PPh)(CH2PC6H4)](4). (1) and
(2) were synthesized by chemical oxidation method with TMNO as
initiator at 0. (3) and (4) were synthesized by thermolytic
method. Complexes have been identified by IR, EA and P-NMR,and
their structures were undertaken by X-ray diffraction method.
The red crystal of (1) crystallized in triclinic space group P1,
a= 10.34(2), b=12.223(2), c= 12.743(3),final Rf= 0.023 for 4813
observed reflections The molecule has a monosubstituted biunit
structure with an inversion centerat the middle point of the
carbon-carbon double bond. The red crystal of (2) crystallized
in orthorhombic space group Pbcn,a=16.179(2), b=16.850(3),
c=18.247(3), final Rf=0.028 for 4368 observed re-flections. The
molecule has a bridged ring with a two-fold axisthrough the Fe
atom and Ru atom. The red crystal of (3) crystallized in
monoclinic space group P21, a=12.686(4), b=14.681(4),
c=15.683(3). Rf=0.066 for 5022 observed reflections.The molecule
has a five-memberd chelating ring and a bridged six-membered
ring. The red crystal of (4) crystallized in monoclinic space
group P21/c,a=9.692(4), b=21.477(4), c=25.361(7).final Rf=0.104
for 5807 observed reflect-ions. The molecule are coordinated by
an axial phosphorous atom, two equator-ial phosphorous atoms, a
discrete phenyl group, a phenyl group attached toa phosphorous
atom and seven carbonyl group.
The derivaties of the Metal carbonyl cluster, [{Ru3(CO)11}2(