Synthesis and characterisation of some new complexes of molybdenum(II) and tungsten(II) containing anionic and neutral sulphur donor ligands
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Abstract
The reaction of [WI2(CO)3(NCMe)2] with two equivalents of PEt3 gives the new seven-coordinate complex [WI2(CO)3(PEt3) 2]. Reaction of the complexes [MI2(CO)PEt3) 2] (M= Mo, W) with one equivalents of the dithiolate ligands Na2[S(CH2)nS] (n = 2 and 3) and two equivalents of Na[SPh], gave the new six-coordinate complexes [W{S(CH2)nS}(CO)2(PEt3) 2] (n = 2 and 3) and [W(SPh)2(CO)2(PEt3)2]. Similarly, reaction of [MoI2(CO)3(PEt3) 2] with one equivalent of Na2[S(CH2)2S] gave [Mo{S(CH2)2S}(CO)2(PEt3) 2]. All four thiolate complexes were crystallographically characterised. The reactions of the complexes [MI2(CO)3(PEt3) 2] (M = Mo or W) with one equivalent of Na[acac] gave the seven-coordinate complexes [MI(acac)(CO)2(PEt3) 2J again both complexes were characterised by X-ray crystallography.
The reactions of the di-bromo complexes [MBr2(CO)3NCMe)2] (M = Mo orW) with a slight excess of RS(CH2)2SR (R = Ph or 4-FC6H4) afforded the seven-coordinate complexes [MBr2(CO)3{RS(CH2)2SR}]. The seven-coordinate tungsten complex [WBr2(CO)3 {PhS(CH2)2SPh}] was crystallographically characterised. Similarly, reactions of [WBr2(CO)3(NCMe)2] with two equivalents of RS(CH2)2SR (R = Ph or 4-FC6H4) gave the complexes [WBr(CO)3{RS(CH2)2SR-S} {RS(CH2) 2SR-S,S'} ]Br. Similarly, the reactions of the complex [WBr2(CO)3NCMe)2] with one and two equivalents of Ph2P(S)CH2(S)PPh2 are reported. The reactions of [MBr2(CO)3(NCMe)2] (M = Mo or W) with one equivalent of the trithioether MeS(CH2)2S(CH2)2SMe (TTN) gave [MoBr2(CO)2 {MeS(CH2) 2S(CH2)2SMe-S,S',S"}]and (WBr2(CO)3 {MeS(CH2)2S(CH2)2SMe-S',S'}J. Also described is the synthesis of the complex [MoBr2(CO)2{ttob-S.S',S"}] (ttob = 2,5,8-trith.ia(9]-o-benzenophane).
The reaction of the complex [WI2(CO)(NCMe)(-PhC2Ph2] with one equivalent of MeS(CH2) 2S(CH2) 2SMe (TTN) gave the structurally characterised complex [WI2(CO)(TTN-S,S')(η2-PhC2Ph)]. The complex [WI2(CO)(TTN-S.S')(η2- PhC2Ph)] reacts with one equivalent of [FeI(CO)2Cp] to give the bimetallic complex [Cp(CO)2Fe(TTN-S,S',S'')WI2(CO)(η2-PhC2Ph)]I. The mono(alkyne) complexes [MI(CO)(L-S,S',S'')(η2-RC2R)]I, [Mol(CO)([9]aneS3-S,S',S'')(η2-RC2R)]I and [WBr(CO)(L-S,S',S'')(η2-PhC2Ph)]Br (M = Mo, W; L = ttob, TTN; R = Me, Ph) were successfully prepared and characterised. The complexes [Mol(CO)((9]aneS3-S,S',S'')(η2-PhC2Ph)]I [WI(ttob-S,S', S'')(η2-PhC2Ph)2]I3 were also characterised by Xray crystallography.
The new seven-coordinate cluster complexes [MI2(CO)3(Fe4Cp4S6-S,S')] were prepared by the reaction of [MI2(CO)3(NCMe)2] (M = Mo or W) with one equivalent of [Fe4Cp4S6J. Further reactions with one and two equivalents of Na[SAr] (Ar = Ph or C6H2Me3-2 ,4,6{tmt}) gave the new cluster complexes [MI(SAr)(CO3Fe4Cp4S6-S,S')] and [M(SAr)2(CO)3(Fe4Cp4S6-S,S')]. Also described are the complexes [M(CO)3(Lˆ L-P,P')Fe4Cp4S6-S,S'')]2I (LˆL = dppe or dppr) and the bis(alkyne) cluster complexes [WI(CO)(Fe4Cp4S6-S,S')(η2-RC2R)2]I (R = Me or Ph).
All new complexes described have been characterised by elemental analysis(C, H, N and S), infra red and 1H NMR spectroscopy, and in selected cases, 13C NMR and Mössbauer spectroscopy.
The reactions of the di-bromo complexes [MBr2(CO)3NCMe)2] (M = Mo orW) with a slight excess of RS(CH2)2SR (R = Ph or 4-FC6H4) afforded the seven-coordinate complexes [MBr2(CO)3{RS(CH2)2SR}]. The seven-coordinate tungsten complex [WBr2(CO)3 {PhS(CH2)2SPh}] was crystallographically characterised. Similarly, reactions of [WBr2(CO)3(NCMe)2] with two equivalents of RS(CH2)2SR (R = Ph or 4-FC6H4) gave the complexes [WBr(CO)3{RS(CH2)2SR-S} {RS(CH2) 2SR-S,S'} ]Br. Similarly, the reactions of the complex [WBr2(CO)3NCMe)2] with one and two equivalents of Ph2P(S)CH2(S)PPh2 are reported. The reactions of [MBr2(CO)3(NCMe)2] (M = Mo or W) with one equivalent of the trithioether MeS(CH2)2S(CH2)2SMe (TTN) gave [MoBr2(CO)2 {MeS(CH2) 2S(CH2)2SMe-S,S',S"}]and (WBr2(CO)3 {MeS(CH2)2S(CH2)2SMe-S',S'}J. Also described is the synthesis of the complex [MoBr2(CO)2{ttob-S.S',S"}] (ttob = 2,5,8-trith.ia(9]-o-benzenophane).
The reaction of the complex [WI2(CO)(NCMe)(-PhC2Ph2] with one equivalent of MeS(CH2) 2S(CH2) 2SMe (TTN) gave the structurally characterised complex [WI2(CO)(TTN-S,S')(η2-PhC2Ph)]. The complex [WI2(CO)(TTN-S.S')(η2- PhC2Ph)] reacts with one equivalent of [FeI(CO)2Cp] to give the bimetallic complex [Cp(CO)2Fe(TTN-S,S',S'')WI2(CO)(η2-PhC2Ph)]I. The mono(alkyne) complexes [MI(CO)(L-S,S',S'')(η2-RC2R)]I, [Mol(CO)([9]aneS3-S,S',S'')(η2-RC2R)]I and [WBr(CO)(L-S,S',S'')(η2-PhC2Ph)]Br (M = Mo, W; L = ttob, TTN; R = Me, Ph) were successfully prepared and characterised. The complexes [Mol(CO)((9]aneS3-S,S',S'')(η2-PhC2Ph)]I [WI(ttob-S,S', S'')(η2-PhC2Ph)2]I3 were also characterised by Xray crystallography.
The new seven-coordinate cluster complexes [MI2(CO)3(Fe4Cp4S6-S,S')] were prepared by the reaction of [MI2(CO)3(NCMe)2] (M = Mo or W) with one equivalent of [Fe4Cp4S6J. Further reactions with one and two equivalents of Na[SAr] (Ar = Ph or C6H2Me3-2 ,4,6{tmt}) gave the new cluster complexes [MI(SAr)(CO3Fe4Cp4S6-S,S')] and [M(SAr)2(CO)3(Fe4Cp4S6-S,S')]. Also described are the complexes [M(CO)3(Lˆ L-P,P')Fe4Cp4S6-S,S'')]2I (LˆL = dppe or dppr) and the bis(alkyne) cluster complexes [WI(CO)(Fe4Cp4S6-S,S')(η2-RC2R)2]I (R = Me or Ph).
All new complexes described have been characterised by elemental analysis(C, H, N and S), infra red and 1H NMR spectroscopy, and in selected cases, 13C NMR and Mössbauer spectroscopy.
Details
| Original language | English |
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| Award date | 1997 |