| Popis: |
Some benzo-crown ethers substituted in the arene ring are described, e.g. some 15-X-substituted benzo-[15-crown-5] ethers [1; X = I, CHO, CH2OH, CH2CI, CH2Ph2(Q), or CH2PBut2(Q′)] : 18-iodobenzo-[18-crown-6](2; X = I) and 15-iodo-16-methylbenzo-[15-crown-51](3; X = I) are also described. We have failed, however, to lithiate or to prepare a Grignard derivative of a benzo-crown ether. The model phosphines PR2[C6H3(OMe)2-3.4][4; R = Ph(L) or But(L′)] have also been synthesized. Reduction of (1; X = CHO) by Li[AlH4] gives, in addition to (1; X = CH2OH), a dicrown ether dibenzyl ether derivative (5; X = H). Similar reduction of 15-formyl-16-methylbenzo-[15-crown-5](3; X = CHO) gives only a dicrown diphenylmethane derivative (6). The chloromethyl derivatives react with Li[PPh2] to give the corresponding phosphines (4; R = Ph) and (1; X = CH2PPh2). and with PBut2H + I– followed by base (Na[OH]) their But analogues. Adducts of the sub-stituted crown ethers (1; X = CHO, Me, or I) with Na[SCN] have been prepared and some conductimetric studiesmade of complex formation with Nal. Complexes of the phosphines L, L′, Q, or Q′ of the types trans-[MCl(CO)-(phosphine)2](M = Rh or Ir), trans-[IrCl2H(CO)Q2], and trans-[IrMe(Cl)I(CO)Q2](also with L) have been prepared. The complex [PdCl2(NCPh)2] reacts with ether Q or L to give [PdCl2Q2] or [PdCl2L2](cis+trans isomers). When treated with Na[O2CMe] in 2-methoxyethanol, [PdCl2L2] undergoes cyclometallation to give [[graphic omitted]Ph2-2)(OMe)2-4,5}2Cl2](8; R = Ph, M = Pd). The complex [PdCl2(NCPh)2] with the bulky crown phosphine Q′ gives a mixture of trans-[PdCl2Q′2] and the corresponding cyclometallated complex; the complex (8; R = But, M = Pd) has also been prepared. A similar but more extensive series of platinum complexes has been made including mononuclear species formed by splitting the chloride-bridged systems with PPh3. Infrared, 1H and 31P n.m.r., and mass spectral data are given. |
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