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。
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.