Novel complexes of Molybdenum and Tungsten in materials chemistry
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Abstract
The reactions of [MI2(CO)3(NCMe)2] {M = Mo or W} with two equivalents of the
fluorescent ligand, 4,5-dihydro-(2H)-l-phenyl-3-(p-cyanophenyl)-5-(p-benzoic acid)-pyrazole (C23H17N3O2) , gave the new seven co-ordinate complexes
[MI2(CO)3(C23H17N3O2)2] {M =Mo or W}. The fluorescence of the complexes was found to be very similar to that of the free ligand. The reaction of [Mo(CO)6] with one equivalent of C23H17N3O3 gave the new six co-ordinate fluorescent complex,
[Mo(CO)5(C23H17N3O2)]. The complexes [Mo(CO)5(L)] and [MoI2(CO)3(L)2 ] {Lfluorescent ligand} exhibited third-order nonlinear optical effects.
The novel 1,2-dithiolene complexes, [W(X)(CO)2(L)] {X = dmit, mnt or bdt, L = (PEt3)2,(PPh3)2 or dppe; X = TTFS4 , L = (PPh3) 2 } were prepared and fully characterised. The structures of the complexes [W(dmit)(CO)2(L)] {L = (PEt3)2} and [W(bdt)(CO)2(L)] {L = (PEt3)2 and dppe} were determined by X-ray crystallography. The previously reported complex [WI2(CO)3(PEt3)2] was synthesised by a new route and the structure determined by X-ray crystallography
The reactions of 3-bromothiophene with a range of Grignard reagents of the type
[Ph(CH2)nMgBr] and [PhO(CH2)nMgBr] {n = 1-6} were investigated. The subsequent reactions of the arene-substituted thiophenes with the complexes fac-[M(CO)3(NCMe)2] were studied. The reaction of [M(CO)6) and fac-[M(CO)3(NCMe)3] with thiophene-3- acetonitrile are also described.
The new seven co-ordinate complexes [WI2(CO3(3-NCCH2 {SC4H3 } )(L)] {L = PPh3, or AsPh3 } were synthesised by the reaction of [WI2(CO)3(NCMe)2] with one equivalent of L {L = PPh3 or AsPh3} followed by the reaction with one equivalent of thiophene-3- acetonitrile. The reaction of [WI2(CO)3(NCMe)2) with two equivalents of thiophene-3- acetonitrile gave the complex, [WI2(CO)3(3-NCCH2 {SC4H3 } ) 2] , which was galvanostatically electropolymerised, and the electrochemistry of both the monomer and the polymer were studied.
All the new complexes have been characterised by elemental analysis (C, H, N and S), infrared spectroscopy, 1 H NMR spectroscopy, and in selected cases, 13 C and 31P NMR, UV / visible spectroscopy and cyclic voltammetry
fluorescent ligand, 4,5-dihydro-(2H)-l-phenyl-3-(p-cyanophenyl)-5-(p-benzoic acid)-pyrazole (C23H17N3O2) , gave the new seven co-ordinate complexes
[MI2(CO)3(C23H17N3O2)2] {M =Mo or W}. The fluorescence of the complexes was found to be very similar to that of the free ligand. The reaction of [Mo(CO)6] with one equivalent of C23H17N3O3 gave the new six co-ordinate fluorescent complex,
[Mo(CO)5(C23H17N3O2)]. The complexes [Mo(CO)5(L)] and [MoI2(CO)3(L)2 ] {Lfluorescent ligand} exhibited third-order nonlinear optical effects.
The novel 1,2-dithiolene complexes, [W(X)(CO)2(L)] {X = dmit, mnt or bdt, L = (PEt3)2,(PPh3)2 or dppe; X = TTFS4 , L = (PPh3) 2 } were prepared and fully characterised. The structures of the complexes [W(dmit)(CO)2(L)] {L = (PEt3)2} and [W(bdt)(CO)2(L)] {L = (PEt3)2 and dppe} were determined by X-ray crystallography. The previously reported complex [WI2(CO)3(PEt3)2] was synthesised by a new route and the structure determined by X-ray crystallography
The reactions of 3-bromothiophene with a range of Grignard reagents of the type
[Ph(CH2)nMgBr] and [PhO(CH2)nMgBr] {n = 1-6} were investigated. The subsequent reactions of the arene-substituted thiophenes with the complexes fac-[M(CO)3(NCMe)2] were studied. The reaction of [M(CO)6) and fac-[M(CO)3(NCMe)3] with thiophene-3- acetonitrile are also described.
The new seven co-ordinate complexes [WI2(CO3(3-NCCH2 {SC4H3 } )(L)] {L = PPh3, or AsPh3 } were synthesised by the reaction of [WI2(CO)3(NCMe)2] with one equivalent of L {L = PPh3 or AsPh3} followed by the reaction with one equivalent of thiophene-3- acetonitrile. The reaction of [WI2(CO)3(NCMe)2) with two equivalents of thiophene-3- acetonitrile gave the complex, [WI2(CO)3(3-NCCH2 {SC4H3 } ) 2] , which was galvanostatically electropolymerised, and the electrochemistry of both the monomer and the polymer were studied.
All the new complexes have been characterised by elemental analysis (C, H, N and S), infrared spectroscopy, 1 H NMR spectroscopy, and in selected cases, 13 C and 31P NMR, UV / visible spectroscopy and cyclic voltammetry
Details
| Original language | English |
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| Award date | 1996 |