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Metal complexes of mercaptophosphines

G. Schwarzenbach

Tech. Hochsch., Zürich, Switzerland


Abstract: The amphoteric mercaptophosphines R3-xP(CH2CH2SH)x (x = 1, 2, 3; R = Ph or Et), prepd. from ethylene sulfide and the corresponding alkali phosphides in liquid NH3, formed polynuclear insol. complexes with the cations of Group Ib-IVb metals and d6-d9 transition metals. Cryst. diamagnetic 1:2 and 1:1 complexes were only obtained from the d8 cations Ni2+, Pd2+, and Pt2+. The planar complexes trans-M[SCH2CH2P(CH2CH2SH)x-1R3-x]2 (I) [x = 1, 2, 3; M = Ni (red), Pd (yellow), Pt (pale yellow)] contained 2 5-membered chelate rings with S-M-P linkages. The free SH groups of I (x = 2, 3) were deprotonated with NaOH. With MeHgOH, I (x = 3, M = Ni) formed the red cryst. Ni[SCH2CH2P(CH2CH2SHgMe)2]2. In the binuclear complexes M2[(SCH2CH2)2PR]2 (M = Ni, Pd, Pt) and Ni2[(SCH2CH2)2PCH2CH2SH]2 (II) each M was surrounded by 1 P and 3 S atoms in a nearly square planar arrangement, the 2 squares being angular-bridged by 2 3-coordinated S atoms. II with NaOH gave the polynuclear Na[NiP(CH2CH2S)3]. The trans-Ni(SCH2CH2PEt2)2 (III) was protonated by 60% HClO4 to give [cis-Ni(HSCH2CH2PEt2)2]2+ (IV). By dilg. a soln. of IV, the yellow cis-Ni(SCH2CH2PEt2)2 was pptd. which rearranged rapidly into the red III. Dissolving III in aq. Ni2+ soln. gave the trinuclear [Ni3(SCH2CH2PEt2)4]2+ contg. the ligands in cis-position with 4 bridging 3-coordinated S atoms.

Full paper in Portable Document Format: 193a200.pdf (in German)


Chemical Papers 19 (3) 200–208 (1965)

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