Insights into the κ-P,N Coordination of 1,3,5-Triaza-7-phosphaadamantane and Derivatives: κ-P,N-Heterometallic Complexes and a (15)N Nuclear Magnetic Resonance Survey

[Image: see text] Complexes {[(PTA)(2)CpRu-μ-CN-1κC:2κ(2)N-RuCp(PTA)(2)-ZnCl(3)]}·2DMSO (13) {[ZnCl(2)(H(2)O)]-(PTA-1κP:2κ(2)N)(PTA)CpRu-μ-CN-1κC:2κ(2)N-RuCp(PTA)(PTA-1κP:2κ(2)N)-[ZnCl(2)(H(2)O)]}Cl (14), [RuCp(HdmoPTA)(PPh(3))(PTA)](CF(3)SO(3))(2) (20), [RuCp(HdmoPTA)(HPTA)(PPh(3))](CF(3)SO(3))(3) (21), and [RuCp(dmoPTA)(PPh(3))(PTA)](CF(3)SO(3)) (22) were obtained and characterized, and their crystal structure together with that of the previously published complex 18 is reported. The behavior of the 1,3,5-triaza-7-phosphatricyclo[3.3.1.13,7]decane (PTA) and 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (dmoPTA) ligands against protonation and κN-coordination is discussed, on the basis of (15)N nuclear magnetic resonance data collected on 22 different compounds, including PTA (1), HdmoPTA (7H), and some common derivatives as free ligands (2–6 and 8), along with mono- and polymetallic complexes containing PTA and/or HdmoPTA (9–22). (15)N detection via (1)H–(15)N heteronuclear multiple bond correlation allowed the construction of a small library of (15)N chemical shifts that shed light on important features regarding κN-coordination in PTA and its derivatives.