Add time:08/07/2019         Source:sciencedirect.com

Piperidinium hexachlororhodate(III) monohydrate undergoes a rapid reaction with piperidine in refluxing benzene to form trichloro tris(piperidine) rhodium(III) and piperidine hydrochloride. At no time during this investigation, however, was a tetrakis(piperidine)-rhodium species detected. Thus the prolonged refluxing either of a piperidinium hexachlororhodate(III) monohydrate-piperidine-benzene suspension, or of a suspension of piperidinium hexachlororhodate(III) monohydrate in pure piperidine, yields primarily piperidine hydrochloride and rhodium(III) oxide. Ammonium hexachloroplatinate(IV), when subjected to refluxing piperidine for periods ranging from 30 min to 135 hr, reacts to form chloro tris(piperidine) platinum(II) chloride and piperidine hydrochloride. Far i.r. assignments are given for chloro tris(piperidine) platinum(II) chloride and for trichloro tris(piperidine) rhodium(III); and it is concluded from the far i.r. data that the trichloro tris(piperidine) rhodium(III) comprised both 1,2,6- and 1,2,3-isomers, with the former being predominant. No evidence was found during this study for the supposed tetrakis(piperidine) platinum(II) chloride reported by Druding and Shupack; and it is noted that these investigators themselves did not present any evidence to substantiate the synthesis of said compound. The fact that a tetrakis(piperidine) complex has yet to be established for either Rh(III) or Pt(II) is attributed to steric hindrance.

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