Title: Novel chemistry of the aromatic P3C2tBu2 anion and its derivatives
Description: Novel chemistry of the aromatic 
3,5-di-t-butyl-1,2,4-tri-phosphacyclopentadienyl P3C2tBu2 anion and its derivatives
Abstract
Tri-phospholyl complexes of the coinage metals Cu() and Au() and the group 12 metals Cd() and Hg() have been isolated and structurally characterized. The binuclear complex [Cu(PMe3)2(-P3C2tBu2)2Cu(PMe3)2] was obtained via the isolated intermediate  [Cu(PMe3)2(-P3C2tBu2)(-I)Cu(PMe3)2]. The Cu-ring bonding is in a -fashion via one of the two adjacent P centres of the P3C2tBu2 ring, which is in contrast to [Cu(5-C5H5)PR3]. The ion pair [Au(PEt3)2][Au(1-P3C2tBu2)2] has been synthesized by treatment of KP3C2tBu2 with [AuCl(PEt3)]. Treatment of KP3C2tBu2 with CdCl2 gave an insoluble powder, which by subsequent treatment with pyridine afforded [Cd(1-P3C2tBu2)2(NC5H5)3]. A completely different product [{HgP6C4tBu4}3] was obtained from HgCl2 and KP3C2tBu2, which is believed to be formed via the unisolated intermediate [Hg(1-P3C2tBu2)2], which underwent a [2+2] cycloaddition reaction to give the trimer [{HgP6C4tBu4}3]. Light exposure of [{HgP6C4tBu4}3] in solution cleanly gave the hexa-phosphapentaprismane P6C4tBu4 via  extrusion of elemental Hg. All these complexes were fully characterized by multi-nuclear NMR spectroscopy and by single crystal X-ray diffraction studies. 
P6C4tBu4 reacts with chalcogens (S, Se and Te) to give MP6C4tBu4 (M = S, Se or Te) by insertion of the chalcogen into the P-P bond between the two five membered rings. The obtained products were fully characterized by multi-nuclear NMR spectroscopy and in the case of TeP6C4tBu4 by a single crystal X-ray diffraction study. These facile insertions were an incentive to study further reactions with heavier carbene species MR2 (M = Ge, Sn or Pb), which gave the expected products MR2P6C4tBu4  (M = Ge, Sn or Pb), by insertion into the P-P bond between the two five membered rings. The resulting compounds MR2P6C4tBu4 (M = Ge, Sn or Pb) were fully characterized by multi-nuclear NMR spectroscopy and by single crystal X-ray diffraction studies. In a similar manner, treatment of [Pt(2-C2H4)(PPh3)2] with P6C4tBu4 gave [Pt(PPh3)2P6C4tBu4] by insertion of the {Pt(PPh3)2} fragment  rather than coordination. Interestingly, insertion of Pt(II) concomitant with migration of Cl to a P atom occurred by treatment of P6C4tBu4 with [{PtCl2(PMe3)}2] to give [PtCl(PMe3)P6C4tBu4Cl]. Similar insertion of Pt(II) and Cl migration took place by treatment of P6C4tBu4 with [PtCl2(4-COD)] to give [{PtClP6C4tBu4Cl}2] and [PtCl(P6C4tBu4)P6C4tBu4Cl]. All complexes were fully characterized by multi-nuclear NMR spectroscopy and single crystal X-ray diffraction studies. 
Tri-phosphaferrocenes [Fe(5-P3C2tBu2)(5-C5R5)] (R= H or Me) react with one equivalent of BuLi to give the very air and moisture sensitive complexes [LiFe(4-P2C2tBu2PBu)(5-C5R5)] (R= H or Me) by nucleophilic attack of the butyl anion on one P atom of the adjacent pair in the P3C2tBu2 ring. Both complexes have been characterised by multi-nuclear NMR spectroscopy and in the case of [LiFe(4-P2C2tBu2PBu)(5-C5Me5)] by a single crystal X-ray diffraction study, which showed an unusual dimeric solid state structure. Treatment of [LiFe(4-P2C2tBu2PBu)(5-C5R5)] (R= H or Me) with MeI gave the zwitterionic complexes [Fe(4-P2C2tBu2PBuMe)(5-C5R5)] (R= H or Me) by electrophilic attack of MeI on the alkylated P(33) of the P2C2tBu2PBu ring. Both complexes have been characterised by multi-nuclear NMR spectroscopy and by single crystal X-ray diffraction studies. Treatment of [LiFe(4-P2C2tBu2PBu)(5-C5R5)] (R = H or  Me) with an ether solution of HCl gave [Fe(4-P3C2tBu2BuH)(5-C5R5)] (R = H or  Me) in which the electrophilic attack of the proton occurred on the C adjacent to the alkylated P(33) of the P2C2tBu2PBu ring. Both products were fully characterized by multi-nuclear spectroscopy and in the case of [Fe(5-P3C2tBu2BuH)(5-C5Me5)]  by a single crystal X-ray diffraction study. 
A new convenient method of preparation of LiP2C3tBu3 has been developed by treatment of tri-phosphabenzene P3C3tBu3 with BuLi via the isolated intermediate LiP3C3tBu3Bu, which was obtained by nucleophilic attack of the Bu anion on a P centre in the P3C3tBu3 ring. Pure [Fe(5-P2C3tBu3)(5-C5Me5)] has been isolated and fully characterized as well as its square planar Pt(II) adduct trans-[PtCl(PMe3){Fe(5-P2C3tBu3)(5-C5Me5)}] also characterized by multi-nuclear NMR spectroscopy.