194208-79-2

Upstream product

• 143406-34-2 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis(3-oxa-butyloxy)calix[4]arene 
• 157432-87-6 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 
• 194208-78-1 5,11,17,23-tetra-tert-butyl-25,27-bis(diphenylphosphinoylmethoxy)-26,28-bis(3-oxabutyloxy)calix[4]arene 

Downstream Products

• 346001-53-4 (η3-2-methylallyl)-(P,P'-[5,11,17,23-tetra-tert-butyl-25,27-bis(2-diphenylphosphinomethoxy)-26,28-bis(3-oxabutyloxy)calix[4]arene])palladium(II) tetrafluoroborate 

Relevant academic research and scientific papers

Capping calixarenes with metallodiphosphine fragments: Towards intracavity reactions

The co-ordinative properties of four disubstituted 5,11,17,23-tetra-tert-butyl-25,27-di-RCH 2O-26,28-bis(diphenylphosphinomethoxy)calix[4]arenes [R = C(O)NEt2 L1, C(O)OEt L2, (A)-C(O)NHCH(Me)Ph L3 or CH2OMe L4] have been investigated. Compound L1 reacted with [Au(thf)(SC4H8)]BF4 (thf = tetrahydrofuran, SC4H8 = tetrahydrothiophene) and AgBF4 to yield the chelate complexes [AuL1]BF4 1 and [AgL1]BF4 2, respectively. Reaction of L1 with trans-[PtH(Cl)(PPh3)2] resulted in quantitative formation of trans-[PtH(Cl)L1] 3 in which the platinum hydrogen bond is partially encapsulated within the calixarene cavity. The structurally related cationic complexes [PtH(PPh3)Li]BF4 (Li = L1 4, L3 5 or L4 6), having a PPh3 ligand trans to the hydrido ligand, were obtained in high yield by treating trans-[PtH(thf)(PPh3)2]BF4 with diphosphine L1. Abstraction of the chloride ion from 3 with AgBF4 gave [PtH(L1)]BF4 7, a complex in which the calixarene behaves as a tridentate P2Oamide ligand and in which the metal plane caps one end of the calixarene tunnel. Reaction of 7 with PPh3 resulted in substitution of the co-ordinated amide to form 4, while reaction with 4,4′-bipyridine gave the binuclear complex [(L1)HPt(4,4′-bipy)PtH(L1)][BF4] 2 8. Reaction of trans-[PtH(Cl)(PPh3)2] with Li resulted in a mixture of complexes of general formula [PtH(PPh3)Li]Cl (type A) and [PtH(Cl)Li] (type B). The A:B ratio depends on the co-ordinating ability of the R groups, since these act as internal solvent molecules in promoting PPh3 substitution. For R groups containing strong donors, eg. as in L1 and L2, complexes of type B are favoured; with L4 the reaction leads selectively to [PtH(PPh3)L4]Cl, no B-type complex being formed. In at least one case (L3) it was shown that complexes of type A may be converted into the B type. Reaction of 7 with dimethyl acetylenedicarboxylate gave the insertion product trans-P,P′-[Pt(MeO2CC=CHCO2Me)L1]BF 4 where the two amides compete for co-ordination. Complex 7 reacted instantaneously with tetracyanoethylene (tcne) to yield the platinum(0) complex [Pt(tcne)L1] for which NMR spectra suggest fast flipping of the co-ordination plane between amides. In contrast to [Pt(MeO2CC=CHCO2Me)L1]BF4, strong tridentate P2O co-ordination abounds in the rhodium carbonyl complexes [Rh(CO)Li]BF4 (Li = L1 or L3) obtained from [Rh(CO)2(thf)2]BF4 and the corresponding diphosphines.