A series of racemic and optically pure aminoalkylferrocenyldichlorophosphanes has been prepared by reaction of phosphorus trichloride with the corresponding lithiated aminoalkylferrocene precursors. Crystal structures of racemic 1-dichlorophosphanyl-2-N,N-dimethylaminomethylferrocene, racemic 1-dichlorophosphanyl-2-N,N-dimethylaminomethyl-3-triphenylsilylferrocene and (S)-N,N-dimethyl-1-[(R)-2-(dichlorophosphanyl)ferrocenyl]ethylamine reveal short intramolecular N[dot dot dot]P distances, which are suggestive of weak N --> P dative bonds. The aminoalkylferrocenyldichlorophosphanes can be used for the preparation of the corresponding primary phosphanes, one of which was characterised by X-ray crystallography. Optically pure (R)-N,N-dimethyl-1-[(S)-2-(phosphanyl)ferrocenyl]ethylamine can easily be lithiated twice to give the first enantiomerically pure lithium-phosphorus closo cluster compound, which was also structurally characterised.

Enantiomerically pure (R P ,R P )-and (R P ,S P )-1,2-bis[1-adamantyloxy-(-)-menthyloxyphosphanyl]-closo-dicarbaborane(12), 1,2-bis[bis(-)-menthyloxyphosphanyl]-closo-dicarbaborane(12) and 1,2-bis[bis(4-tert-butylphenyloxy)phosphanyl]-closo-dicarbaborane(12) were synthesised by the reaction of dilithiated 1,2-dicarba-closo-dodecaborane(12) with two equivalents of the corresponding chlorophosphite. The phosphonites are stable towards epimerisation, oxygen and water. P···P through-space coupling was observed, and the 3 J PP cou-

Li12P6: The first two primary aminoalkyl(phosphanyl)ferrocene complexes 2‐(N,N‐Dimethylaminomethyl)phosphanylferrocene (1) and N,N‐dimethyl‐1‐(2‐phosphanylferrocenyl)ethylamine (2) are prepared. Compound 1 readily undergoes twofold deprotonation with nBuLi to form the first lithium–phosphorus cluster (see picture) which has the structure and electronic properties of a closo cluster according to Wade's rules.

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Diastereomerically pure 1-[1-(1,2-dicarba-closo-dodecaboran(12)yl)chlorophosphanyl]-2-N,N-dimethylaminomethylferrocene ((R P ,S Fc /S P ,R Fc )-3) and enantiomerically pure 12)yl)}chlorophosphanyl]ferrocenyl}ethylamine ((S C ,S P ,R Fc )-4) were prepared by reaction of monolithiated 1,2-dicarba-closo-dodecaborane( 12) and the corresponding racemic or enantiomerically pure aminoalkylferrocenyldichlorophosphanes (1 or (S,R)-2). Two equivalents of 1 also reacted with dilithiated 1,2-dicarba-closo-dodecaborane(12) to yield stereoselectively the R