New Types of Group 4 and 13 Metal Complexes Stabilized by Homo- or Hetero-Donor Functionalized Dicarbollide Ligands: Syntheses, Characterizations, and Structural Studies of [{η5-C2B9H9(D)}(η1-NMe2CH2)]M(NMe2)2(D = CH2NMe2, PPh2; M = Ti, Zr) and [(η1-D)(η1-NMe2CH2)C2B9H10]MMe2(D = CH2NMe2, PPh2; M = Al, Ga)

A series of group 4 and 13 metal complexes coordinated to either a homo- or hetero-donor and a dicarbollyl ligand derived from N,N′- or P,N-chelated ligands were synthesized and characterized. Two homo- and hetero-donor tethered ligands of the type 7,8-(Me2NCH2)(μ-H)(Me2NCH2)-7,8-C2B9H10(DcabNNH, 3) and 7-PPh2-8-Me2NHCH2-7,8-C2B9H10(DcabPNH, 6) were prepared using the standard deborination methods from 1,2-(NMe2CH2)2-1,2-C2B10H10(2) and 1-PPh2-2-Me2NCH2-1,2-C2B10H10(5), respectively. Subsequent reactions of 3with M(NMe2)4(M = Ti, Zr) produced single nitrogen donors involving π,σ-dicarbollides of the type [{η5-C2B9H9(CH2NMe2)}(η1-NMe2CH2)]M(NMe2)2(M = Ti (4), Zr (5)). Structurally similar nitrogen donor stabilized π,σ-dicarbollides of the type [{η5-C2B9H9(PPh2)}(η1-NMe2CH2)]M(NMe2)2(M = Ti (7), Zr (8)) were produced from the reaction of 6with M(NMe2)4(M = Ti, Zr). When group 13 metals were attempted with dissimilar ligands, 3and 6, σ,σ-type complexes were formed with the engagement of two tethered donors at the dicarbollide ligand in an exo-polyhedral manner irrespective of the dissimilar donor properties, nitrogen or phosphine. As a result, a series of group 13 metal complexes bearing ligands 3and 6, [(η1-NMe2CH2)2C2B9H10]MMe2(M = Al (11), Ga (12)) and [(η1-PPh2)(η1-NMe2CH2)C2B9H10]MMe2(M = Al (13), Ga (14)), were prepared by reacting 3and 6with trimethylaluminum (TMA) and trimethylgallium (TMG), respectively. New types of π,σ- and σ,σ-coordination were established by extensive structural studies of each metal complex comprising N,N′- or P,N-chelated dicarbollide: 7, 9, 10, 11, 13, and 14. [ABSTRACT FROM AUTHOR]