This is the peer reviewed version of the following article: [Synthesis and Solid-State Characterization of Platinum Complexes with Hexadentate Amino-and Iminophosphine Ligands, Dalton Trans., 2009, 7701-7716], which has been published in final form at [10.1039/b907737e]. TOC graphic Hexadentate ligands were synthesized from the cis,cis-1,3,5-triaminocyclohexane and coordinated to Pt(0) and Pt(II) precursors. Since the resulting complexes are negligibly soluble, solid-state NMR spectroscopy was

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... pplied to analyse the bonding modes of the hexadentate ligands. Abstract Hexadentate ligands cis,cis-C6H9(N=CHC6H4(PPh2))3 (1) and cis,cis-C6H9(NHCH2C6H4(PPh2))3 (2) were synthesized starting from the cis,cis-1,3,5triaminocyclohexane, and characterized using NMR spectroscopy and single-crystal Xray diffraction. These ligands can bind both Pt (0) and Pt(II) metal centers using either or both of the soft phosphine moieties and the hard amine/imine moieties. In many cases the resulting complexes are negligibly soluble; hence, 31 P and 195 Pt solid-state NMR (SSNMR) spectroscopy was applied to analyse the bonding modes of the hexadentate ligands. The 195 Pt SSNMR spectroscopy of these complexes is particularly challenging, since 1 H-195 Pt cross polarization is extremely inefficient, the 195 Pt longitudinal relaxation times are extremely long and the 195 Pt powder patterns are expected to be quite broad due to platinum chemical shift anisotropy. It is demonstrated that the ultra-wideline 195 Pt SSNMR spectra can be efficiently acquired with a combination of frequency-stepped piecewise acquisitions and cross-polarization/Carr-Purcell Meiboom-Gill (CP/CPMG) NMR experiments. The 195 Pt and 31 P SSNMR data are correlated to important structural features in both Pt (0) and Pt(II) species.