BIDENTATE AND TERDENTATE (P-N-S) COMPLEXES OF A NEW THIOETHER AZINE PHOSPHINE ,E-PPH(2)CH(2)C(BU(T))=N-N=C(ME)CH2S(C(6)H(4)ME-4) WITH MOLYBDENUM, TUNGSTEN, OR PLATINUM

Treatment of Z-PPh(2)CH(2)C(Bu(t))=NNH2 with 4-methylphenylthiomethyl methyl ketone gave the thioether azine phosphine ,E-PPh(2)CH(2)C(Bu(t) )=N-N=C(Me)CH2S(C(6)H(4)Me-4) 1, which with H2O2 gave the correspondin g phosphine oxide 2. Treatment of 1 with [Mo(CO)(3)(eta(6)-cht)] or [W (CO)(3)(NCEt)(3)] gave the yellow tricarbonyl complexes ){PPh(2)CH(2)C (Bu(t))=N-N=C(Me)CH2S(C(6)H(4)Me-4}] 3a (Mo) or 3b (W), respectively. Treatment of 1 with [Mo(CO)(4)(nbd)] gave the pale yellow tetracarbony lmolbdenum(0) complex {PPh(2)CH(2)C(Bu(t))=N-N=C(Me)CH2S(C(6)H(4)Me-4) }] 4, in which the ligand 1 is bidentate through P and N. Oxidation of either 3a or 4 with 1 equivalent of bromine gave the orange neutral s even-coordinate dicarbonylmolybdenum(II) complex {PPh(2)CH(2)C(Bu(t))= N-N=C(Me)CH2S(C(6)H(4)Me-4)}] 5, whereas the tungsten complex 3b with 1 equivalent of bromine gave the seven-coordinate tricarbonyltungsten( II) cation h(2)CH(2)C(Bu(t))=N-N=C(Me)CH2S(C(6)H(4)Me-4)}](+) isolated as the PF6 salt 6. Treatment of 1 with [PtCl2(NCMe)(2)]gave the yello w dichloroplatinum(II) complex {PPh(2)CH(2)C(Bu(t))=N-N=C(Me)CH2S(C(6) H(4)Me-4)}] 7, in which 1 is bidentate through P and N. When 7 was tre ated with NH4PF6 in methanol it gave the terdentate salt h(2)CH(2)C(Bu (t))=N-N=C(Me)CH2S(C(6)H(4)Me-4)}]PF6 8a. Deprotonation of 7 with NEt( 3)-NaOH gave the orange neutral chloroplatinum(II) complex l{PPh(2)CH( 2)C(Bu(t))=N-NC(Me)=CHS(C(6)H(4)Me-4)}] 9, containing a terdentate ene -hydrazone phosphine ligand. This neutral complex 9 was reprotonated u sing HBF4 to give the BF4 salt 8b. Treatment of the phosphine 1 with [ PtMe(2)(cod)] gave the white dimethylplatinum(II) complex {PPh(2)CH(2) C(Bu(t))=N-N=C(Me)CH2S(C(6)H(4)Me-4)}] 10, containing the bidentate az ine ligand. Treatment of 10 with Mel gave the white platinum(rv) iodid e salt ){PPh(2)CH(2)C(Bu(t)=N-N=C(Me)CH2S(C(6)H(4)Me-4)}] I 11a in whi ch the azine is terdentate. When 11a was treated with NH4PF6 in MeOH t he PF6 salt 11b was obtained. Treatment of 10 with picric acid gave th e yellow methylplatinum(II) picrate salt N-N=C(Me)CH2S(C(6)H(4)Me-4)}] [OC6H2(NO2)(3)-2,4,6] 12 and methane. Infrared, P-31-[H-1], H-1, and s ome C-13-[H-1] NMR data are given.