十二羰四銥[Ir4(CO)12]與含磷雙牙配子Ph2P(CH2)3PPh2(dppp), Ph2P(CH2)4PPh2, (dppb), Fe(C5H4PPh2)(dppf)經由熱裂法反應共得到七個錯合物[Ir4(CO)8(dppp)2] (1), [Ir4(CO)8(dppp)2](1a), [HIr4(CO)7{Fe(C5H4PPh2)2}{Fe(C5H4PPh2)2(C5H3PPh2)2}](4), [H2Ir4(CO)6{Fe(C5H4PPh2)2(C5H3PPh2)2}](5), [H3Ir4(CO)4{Fe(C5H4PPh2)2(C5H3PPh2)2]}{Fe(C5H4)(C5H4P(Ph)(C6H4))}{P(Ph)(C6H4)}](6), [H4Ir4(CO)4{Fe(C5H3PPh2)(C5H4P(Ph)(C6H4)}2](7) 和[Ir4(CO)8(dppf)2(8)。而[Ir4(CO)12]與三牙配子MeC(CH2PPh2)3, Ph(CH2CH2PPh2)2以TMNO為起始劑經化學氧化法反應可得[Ir4(CO)9MeC(CH2PPh2)3](2)和[Ir4(CO)9Ph(CH2CH2PPh2)2](3)。錯合物(1)、(2)、(3)、(4)、(5)、(6)和(7)以X射線單晶繞射的方法獲得晶體結構。
晶體數據：(1)，單斜晶系，空間群P21/n，a = 12.584(2), b = 38.330(7), c = 13.273(3)A, β = 97.81(3)°，最後Rf = 0.047(9522個繞射點)。(2)，直方晶系，空間群P212121, a = 13.719(2), b = 17.228(3), c = 24.317(3)A，最後Rf = 0.033(4105個繞射點)。(3)，三斜晶系，空間群P1, a = 11.275(5), b = 11.493(7), c = 18.885(9)A, α = 83.90(5), β = 77.43(4), γ = 63.56(4)°，最後Rf = 0.046(5617個繞射點)。(4)，單斜晶系，空間群C2/c, a = 29.583(5), b = 27.995(4), c = 21.915(5)A, β=120.00(2)°，最後Rf=0.037（6203個繞射點)。(5)，三斜晶系，空間群P1, a=13.868(4), b=15.110(2), c=18.440(3)A, a=79.53(1), β=82.52(2), r=63.66(2)°，最後Rf=0.030(8753個繞射點）。(6)，單斜晶系，空間群P21/n, a=11.131(2), b=22.747(2), c=25.222(8)A,β=100.22(2)°, 最後Rf=0.033(6836個繞射點)。(7)，單斜晶系，空間群P21/c, a=19.153(5), b=10.933(4), c=33.339(4)A, =93.49(2)°，最後Rf=0.040(7074個繞射點)。
前面敘述的九個錯合物包含了三、四、五、六、八取代，顯示了金屬簇配位型態的多樣化。各結構的特徵將於論文內容中予以討論。

The reactions of [Ir4(CO)12] with Ph2P(CH2)3PPh2 (dppp)、Ph2P(CH2)4PPh2(dppb) or Fe(C5H4PPh2)2(dppf) by thermolytic method yield seven complexes: [Ir4(CO)8(dppp)2](1),[Ir4(CO)8(dppb)2](1a),[HIr4(CO)7{Fe(C5H4PPh2)2}{Fe(C5H4PPh2)(C5H3PPh2)}](4),[H2Ir4(CO)6{Fe(C5H4PPh2)(C5H3PPh2)}2](5),[H3Ir4(CO)4{Fe(C5H4PPh2)(C5H3PPh2)}{Fe(C5H4)(C5H4P(Ph)(C6H4))}{P(Ph)(C6H4)}](6),[H4Ir4(CO)4{Fe(C5H3PPh2)(C5H4P(PH)(C6H4))}2](7)and[Ir4(CO)8(dppf)2](8).Reactions of [Ir4(CO)12]with MeC(CH2PPh2)3 or Ph(CH2CH2PPh2)2 by the chemical oxidation method with TMNO as initiator yield [Ir4(CO)9MeC(CH2PPh2)3](2) and [Ir4(CO)9Ph(CH2CH2PPh2)2](3).Crystal structures of the complexes (1)、(2)、(3)、(4)、(5)、(6)、and (7) have been determined by the X-ray diffraction method.
Crystal data: (1), space group P 21/n, a=12.584(2), b=38.330(7), c=13.273(3)A. β=97.81(3)° Final Rf=0.047 for 9522 observations. (2), space proup P 212121, a=13.719(2), b=17.228(3), c=24.317(3)A . Final Rf=0.033 for 4105 observations.(3), space group P I, a=11.275(5), b=11.493(7), c=18.885(9)A, a=83.90(5),□=77.43(4), r=63.56(4). Final Rf=0.046 for 5617observations.(4), space group C 2/c, a=29.583(5), b=27.995(4), c=21.915(5)A, b=120.00(2)°. Final Rf=0.037 for 6203 observations.(5), space group P 1, a=13.868(4), b=15.110(2), c=18.440(3)A, a=79.53(1), b=82.52(2), r=63.66(2)°. Final Rf=0.030 for 8753 observations. (6), space group P 21/n, a=11.131(2), b=22.747(2), c=25.222(8)A, β=100.22(2)°,Final Rf=0.033 fo 6836 observations.(7), space group P 21/c, a=19.153(5), b=10.933(4), c=33.339(4)A, β=93.49(2)°. Final Rf=0.040 for 7074 observations.
The molecular structures of these tri-, tetra-, penta-, hexa-and octa-substituted derivatives have been discussed in the discussion section.