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.

Complexes {[(PTA) 2 CpRu-μ-CN-1 κC :2 κ 2 N -RuCp(PTA) 2 -ZnCl 3 ]}·2DMSO ( 13 ) {[ZnCl 2 (H 2 O)]-(PTA-1κ P :2κ 2 N )(PTA)CpRu-μ-CN-1κ C :2κ 2 N -RuCp(PTA)(PTA-1κ P :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 κ N -coordination is discussed, on the basis of 15 N nuclear magnetic resonance data collected on 22 different compounds, including PTA ( 1 ), HdmoPTA ( 7 H), 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 κ N -coordination in PTA and its derivatives.