DFT-optimized structures (Jaguar 5.0, B3LYP/LACVP**) for (A) doublet [PhBPiPr3]Mn(N) and (B) quartet [PhBPiPr3]Mn(N). Selected bond distances (Å) and angles (deg) for (A): Mn–N 1.50; Mn–P 2.35, 2.41, 2.45; N–Mn–P 112.1, 122.3, 127.5; P–Mn–P 94.8, 95.6, 97.2. For (B): Mn–N 1.62; Mn–P 2.48, 2.49, 2.60; N–Mn–P 103.9, 109.3, 155.3; P–Mn–P 89.9, 90.5, 91.2.