Coordination Chemistry Reviews 248 (2004) 955–993 Review Coordination chemistry of 1,3,5-triaza-7-phosphaadamantane (PTA) Transition metal complexes and related catalytic, medicinal and photoluminescent applications Andrew D. Phillips a , Luca Gonsalvi a , Antonio Romerosa b , Francesco Vizza a , Maurizio Peruzzini a,∗ a Consiglio Nazionale delle Ricerche, Istituto di Chimica del Composti Organometallici (CNR-ICCOM), Via Madonna del Piano, Area di Ricerca di Firenze, 50019 Sesto Fiorentino, Firenze, Italy b Área de Qu´ ımica Inorgánica, Facultad de Ciencias Experimentales, Universidad de Almer´ ıa, 04071 Almer´ ıa, Spain Received 18 January 2004; accepted 23 March 2004 Available online 27 July 2004 Contents Abstract ................................................................................................................................ 956 1. Introduction ........................................................................................................................ 956 2. Synthesis and derivatization of 1,3,5-triaza-7-phosphaadamantane (PTA) .................................................................. 956 3. Physical properties of PTA and related PTA derivatives .................................................................................. 959 4. Transition metal complexes involving PTA and related PTA derivatives ................................................................... 960 4.1. Chromium, molybdenum and tungsten PTA complexes ............................................................................ 960 4.2. Rhenium PTA complexes ...................................................................................................... 966 4.3. Iron and ruthenium PTA complexes ............................................................................................. 967 4.4. Rhodium and iridium–PTA complexes ........................................................................................... 970 4.5. Nickel, palladium and platinum-PTA complexes .................................................................................. 972 4.6. Copper and gold-PTA complexes ............................................................................................... 977 4.7. Mercury-PTA complexes ....................................................................................................... 979 5. Single crystal X-ray diffraction data for transition metal complexes of PTA ................................................................ 980 6. Catalytic properties of PTA transition metal complexes .................................................................................. 981 7. Medicinal applications of PTA complexes ............................................................................................. 987 8. Photoluminescent properties of PTA complexes ........................................................................................ 988 9. Latest developments ................................................................................................................. 991 Acknowledgements ...................................................................................................................... 991 References ............................................................................................................................. 991 Abbreviations: Ac, acetyl; acac, acetylacetonate; bmim, 1-butyl-3-methylimidazolium; Bz, benzyl; CI-MS, chemical impact mass spectrometry; COD, 1,5-cyclooctadiene; Cp, cyclopentadienyl; Cp ∗ , pentamethylcyclopentadienyl; CP MAS, cross-polarization magic angle spinning; Cy, cyclo-C 6 H 11 ; cyep, tris(2-cyanoethyl)phosphine, P(CH 2 CN) 3 ; DAPTA, 3,7-diacetyl-1,3,5-triaza-7-phosphaadamantane; dba, dibenzylideneacetone; DMF, dimethylformamide; DMSO, dimethylsulfoxide; DOPC, dioleoylphosphatidylcholine; dppe, diphenylphosphinoethane; DSR, dimethylsulfoxide reductase; ESI, electrospray ionization; ESMS, electrospray mass spectrometry; FAB-MS, fast atomic bombardment mass spectrometry; FTICR-MS, Fourier transform ion cyclotron resonance mass spectrometry; HE, high energy; hmim, 1-hexyl-3-methylimidazolium; HPNMR, high pressure NMR spectroscopy; Hpy, pirydinium; IC 50 , concentration of sample required to reduce the cell growth by 50% (ng ml -1 ); lb ratio, linear/branched ratio; LE, low energy; Mes, mesityl; MesH, mesitylene; MLCT, metal-to-ligand charge transfer; NBD, norbornadiene; OAc, acetate; OCT, octahedral; omim, 1-octyl-3-methylimidazolium; OTf, triflate, OSO 2 CF 3 ; PE, photoelectron spectroscopy; PET, positron emission tomography; pip, piperidine, NHC 5 H 10 ; PNP, bis(diphenylphosphinoethyl)n-propylamine; PTA, 1,3,5-triaza-7-phosphaadamantane; PTA(H), N-protonated PTA; PTA(R), N-alkylated PTA; (R)PTA, P-alkylated PTA; PTA(O), 1,3,5-triaza-7-phosphaadamantane oxide; PTA(S), 1,3,5-triaza-7-phosphaadamantane sulfide; PTA(Se), 1,3,5-triaza-7-phosphaadamantane selenide; py, pyridine; RAPTA, ruthenium/arene/PTA compounds; S, solubility; SP, square planar; TBP, trigonal bipyramidal; THF, tetrahydrofuran; THT, tetrahydrothiophene; TMEDA, tetramethylethylendiamine; TOF, turnover frequency (TONh -1 ); TON, turnover number (mol product per mol catalyst); tos, toluene-4-sulfonate; TPPMS, sodium triphenylphosphine monosulfonate; TPPTS, trisodium triphenylphosphine trisulfonate; ts, thiosalicylate, SC 6 H 4 COO - ; xs, excess; Y, generic uninegative anion; WGSR, water gas shift reaction ∗ Corresponding author. Tel.: +39-55-522-5289; fax: +39-55-522-5203. E-mail address: mperuzzini@iccom.cnr.it (M. Peruzzini). 0010-8545/$ – see front matter © 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.ccr.2004.03.010