The nature of the phosphorus-metal bond in triphenylphosphine—transition metal complexes (Pd[P(C6H5)3]4, Rh(CO)Cl[P(C6H5)3]2 and Ir(CO)Cl[P(C6H5)3]2. A direct determination of the importance of P3d and PC σ∗ orbitals in ‘back-bonding’ by X-ray emission spectroscopy