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.

No abstract

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

No abstract

1,2‐Bis(chloroalkoxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12) and 1,2‐bis(amido‐(‐)‐menthyloxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaboranes(12) were synthesised by the reaction of dilithiated 1,2‐dicarba‐closo‐dodecaborane(12) with the corresponding dichloro‐ or chloroamidophosphite. For 1,2‐bis‐(chloro‐1‐adamantyloxyphosphanyl)‐1,2‐dicarba‐closo‐dodecaborane(12) epimerisation in solution was observed and the free activation enthalpy was determined experimentally and theoretically. An indirect determination of the meso configuration was obtained by formation of the corresponding molybdenum tetracarbonyl complex. Chlorido‐bridged dimeric chiral rhodium(I) complexes showing planar or folded Rh2Cl2 rings were prepared. Density functional calculations indicate that steric and packing factors play a much more significant role than electronic effects in influencing the bending of the rhodium complexes.

No abstract