含磷雙牙、三牙、四牙錳金屬羰基錯合物的合成及結構研究

蕭甯中(Hsiao Ning-Chung)

指導教授 ： 翁春和

國立臺灣師範大學/理學院/化學系/碩士(2002年)

摘要

十羰二錳[Mn2(CO)10]與含磷雙牙配子1,1-雙二苯膦甲烷Ph2P(CH2)PPh2 (dppm)、1,6-雙二苯膦己烷Ph2P(CH2)6PPh2 (dpph)、 [Fe(C5H4PPh2)2] (dppf)、三牙配子二(2-雙二苯膦乙烷基)苯膦Ph2P(CH2)2PPh(CH2)2PPh2 ( pf-pf-pf )及四牙配子三(2-雙二苯膦乙烷基) 膦P(CH2CH2PPh2)3 ( p-pf3 )反應分別生成四個單錳含磷錯合物[Mn(CO)3(dppf)Cl] (1)、[HMn(CO)3(dppf)] (2)、[Mn(CO)3(pf-pf-pf)](3)、 [HMn(CO)2(pf-pf-pf)] (4)與五個雙錳含磷錯合物[Mn2(CO)8(dppm)] (5)、[Mn2(CO)6(dppm)2](6)、[Mn2(CO)6(dppm)(PPh2)](7)、[Mn2(CO)5-
(dppm)2](8)、[H2Mn2(CO)6(dpph)2](9)及一個四錳含磷錯合物
[Mn4(CO)16(p-pf3)] (10)。全部產物皆由熱裂法製得，但化合物(1)亦可由化學氧化法製得。除了以紅外線光譜做初步鑑定外，並以X射線單晶繞射法解析晶體結構。
(1)之黃色晶體屬單斜晶系，空間群P 21/c，a = 11.538(2)Å，b = 19.400(3)Å，c = 14.324(2)Å，β= 93.689(1)° ，最後Rf = 0.034 (4783個繞射點)。Mn-Mn金屬鍵斷裂，被氯取代形成八面體結構。其中二個末端羰基被dppf的二個磷所取代。
(2)之黃色晶體屬三斜晶系，空間群P ‾1，a = 10.0836(6)Å，b = 10.4437(7)Å，c = 17.4610(1)Å，a = 75.413(4)° ，b = 74.462(3)° ，g = 64.480(3)°，最後Rf = 0.050(3174個繞射點)。Mn-Mn金屬鍵斷裂，被氯取代形成八面體結構。其中二個末端羰基被dppf的二個磷所取代。
(3)之黃色晶體屬單斜晶系，空間群C 2/c，a = 17.802(3)Å，b = 14.528(4)Å，c = 31.932(6)Å，β= 93.35(2)°，最後Rf = 0.100 (2664個繞射點)。Mn-Mn金屬鍵斷裂，形成八面體結構。其中三個末端羰基被pf-pf-pf的三個磷所取代。
(4)之黃色晶體屬單斜晶系，空間群P 21/n，a = 8.68(1)Å，b = 30.51(2)Å，c = 12.503(6)Å，β= 100.59(7)°，最後Rf = 0.065 (3304個繞射點)。Mn-Mn金屬鍵斷裂，被氫取代形成八面體結構。其中三個末端羰基被pf-pf-pf的三個磷所取代。
(5)之橘色晶體屬三斜晶系，空間群P ‾1，a = 12.6433 (8)Å ，b = 15.3444(1)Å ，c = 17.8766(1)Å，a = 111.945(3)° ，b = 94.106(3)° ，g = 90.430(3)° ，最後Rf = 0.086(4528個繞射點)。Mn-Mn金屬仍鍵結，維持雙八面體結構。其中每一個金屬各有一個末端羰基被dppm的磷所取代。
(6)之橘色晶體屬三斜晶系，空間群P ‾1，a = 15.7265(2)Å，b = 16.7982(2)Å，c = 21.5220(3)Å，α= 100.9285(6)°、β= 104.6367(6)°、γ= 95.7271(9)°，最後Rf = 0.056(16640個繞射點)。Mn-Mn金屬仍鍵結，維持雙八面體結構。其中四個末端羰基被兩個dppm的四個磷所取代。
(7)之黃色晶體屬直方晶系，空間群P 212121，a = 9.9256 (3)Å ，b = 19.1391(6)Å ，c = 20.4819(7)Å ，最後Rf = 0.045(3433個繞射點)。Mn-Mn金屬仍鍵結，其中dppm與PPh2當架橋。
(8)之黃色晶體屬直方晶系，空間群P bca，a = 18.0646 (5)Å ，b = 19.1777(5)Å ，c = 34.0423(1)Å，最後Rf =0.079(4072個繞射點)。Mn-Mn金屬仍鍵結，其中二個dppm和一個CO當架橋配子。
(9)之黃色晶體屬單斜晶系，空間群P 21/n，a = 12.1610(5)Å ， b = 21.0312(8)Å ，c = 13.6597(6)Å ，b = 90.387(2)° ，最後Rf = 0.078(3420個繞射點)。Mn-Mn金屬鍵斷裂，其中兩個dpph當架橋配子，而形成十八員環結構。
(10)之黃色晶體屬單斜晶系，空間群P 21/n，a = 13.0509(1) Å ，b = 15.2901(1)Å ，c = 30.1268(3)Å ，a = 90.00° ，b = 97.1140(4)°，最後Rf =0.048(10208個繞射點)。Mn-Mn金屬仍鍵結，其中p-pf3當架橋配子。

關鍵字

錳 ； 磷

並列摘要

Manganese carbonyl [Mn2(CO)10] reacts with phosphine ligands Ph2P(CH2)PPh2 (dppm), Ph2P(CH2)6PPh2 (dpph), [Fe(C5H4PPh2)2] (dppf), Ph2P(CH2)2PPh(CH2)2PPh2 (pf-pf-pf) and P(CH2CH2PPh2)3 (p-pf3) yield four mononuclear complexes：[Mn(CO)3(dppf)Cl] (1)、[HMn(CO)3(dppf)] (2)、[Mn(CO)3(pf-pf-pf)](3)、[HMn(CO)2(pf-pf-pf)] (4) and five binuclear complexes：[Mn2(CO)8(dppm)] (5)、[Mn2(CO)6(dppm)2](6)、[Mn2(CO)6- (dppm)(PPh2)](7)、[Mn2(CO)5(dppm)2](8)、[H2Mn2(CO)6(dpph)2](9)、and one tetranuclear complex [Mn4(CO)16(p-pf3)](10). These complexes were prepared by thermolytic method. But compound(1) was also prepared by chemical oxidation method with TMNO as an initiator at 25℃.Complex- es have preliminary been identified by infrared spectra and their structur- es have been determined by single-crystal X-ray diffraction studies.
The yellow crystal of (1) crystallized in monoclinic lattice , space group P 21/c , a = 11.538(2)Å , b = 19.400(3)Å , c = 14.325(2)Å , β= 93.689(1)° , final Rf = 0.034 for 4783 observed reflections . The Mn atom is octahedrally coordinated by three carbonyl ligands (in a facial arrangement) , two phosphorous atoms of dppf , and a chloride.
The yellow crystal of (2) crystallized in triclinic lattice , space group P ‾1 , a = 10.0836(6)Å，b = 10.4437(7)Å , c = 17.4610 (1)Å , a = 75.413 (4)° , b = 74.462(3)° , g = 64.480(3)°, final Rf = 0.050 for 3174 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands (in a facial arrangement), two phosphorous of dppf , and a hydride.
The yellow crystal of (3) crystallized in monoclinic lattice , space group C 2/c , a = 17.802(3)Å , b = 14.528(4)Å , c = 31.932(6)Å , β= 93.35(2)°, final Rf = 0.100 for 2664 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands (in a facial arrangement) , three phosphorous of pf-pf-pf.
The yellow crystal of (4) crystallized in monoclinic lattice , space group P 21/n , a = 8.682(1)Å , b = 30.51(2)Å , c = 12.503(6)Å ,β= 100.59(7)° , final Rf= 0.065 for 3304 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands , three phosphorous of pf-pf-pf.
The orange crystal of (5) crystallized in triclinic lattice , space group P ‾1 , a = 12.6433(8)Å ，b = 15.3444(1)Å , c = 17.8766(1)Å，a = 111.945(3)° , b = 94.106(3)° , g = 90.430(3)°, final Rf =0.086 for 4528 observed reflections. The two Mn atoms are double-octahedrally coordinated by eight carbonyl ligands , two phosphorous of dppm.
The orange crystal of (6) crystallized in triclinic lattice , space group P ‾1, a = 15.7265(2)Å , b = 16.7982(2)Å , c = 21.5220(3)Å ,α= 100.9285(6)°、β=104.6367(6)°、γ=95.7271(9)° , final Rf =0.056 for 16640 observed reflections. The two Mn atoms are double-octahedrally coordinated by six carbonyl ligands , four phosphorous of dppm.
The yellow crystal of (7) crystallized in orthorhombic lattice , space group P 212121 , a = 9.9256(3)Å , b = 19.1391(6)Å , c = 20.4819Å , final Rf=0.045 for 3433 observed reflections. The two Mn atoms are bonded by the bridging dppm and PPh2 ligands.
The yellow crystal of (8) crystallized in orthorhombic lattice , space group P bca , a = 18.0646(5)Å , b = 19.1777(5)Å , c = 34.0423(1)Å , final Rf = 0.079 for 4072 observed reflections. The two Mn atoms are bonded by bridging dppm ligands and one CO ligand.
The yellow crystal of (9) crystallized in monoclinic lattice , space group P 21/n , a = 12.1610(5)Å , b = 21.0312(8)Å , c = 13.6597(6)Å , b = 90.387(2)° , final Rf =0.078 for 3420 observed reflections. The metal-bond of two Mn atoms is broken . The complex has a 18-membered-ring formed by the metals and the bridging dpph ligands.
The yellow crystal of (10) crystallized in monoclinic lattice , space group P 21/n , a = 13.0509(1)Å , b = 15.2901(1)Å , c = 30.1268(3)Å , b = 97.1140(4)° , final Rf =0.048 for 10208 observed reflections. The binuclear Mn pairs are bounded by the bridging p-pf3 ligand.

並列關鍵字

Manganese ； Phosphino

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