Lineare Oligophosphaalkane. XXVI. Funktionalisierte primaere Phosphane in der Clustersynthese-metallassistierte Fragmentierung von Ph2P-CH2-PH2

Article abstract of DOI:10.1016/0022-328X(93)83172-R

On reaction with diironenneacarbonyl the tertiary primary phosphine Ph2PCH2PH2 yields the hydrido cluster (μ₂-H)(μ₂-PHCH2PPh2)Fe3(CO)9 (4).If excess of Fe2(CO)9 is employed in this reaction the P-C-P-bridged Fe4-cluster 5 is formed with loss of hydrogen.At higher temperatures rearrangement of the Fe3(Fe)P-skeleton and phosphinidene fragmentation of the P-C-P backbone of 5 affords the Fe4P spiro compound (μ₄-P)(μ₂,η²-PPh2CH2)Fe4(CO)14 (6) with an edge bridging Ph2-CH2 unit.X-ray structural analysis of 6 (space group P2₁/n) reveals a distorted Fe4P spiro type arrangement.The iron atoms Fe(1) and Fe(3) and the Ph2PCH2 ligand with a short P-C bond (P(1)-C(1) 178.6(7) pm) form a distorted almost planar four-membered Fe2PC ring system.