TRIPOD LIGANDS CONTAINING A MIXED P N/S DONOR SET - SYNTHESIS AND COORDINATION CHEMISTRY/

The preparation of neopentane-based tripod ligands CH3C(CH2X)(CH2Y)(CH (2)Z) 3 (X = NR2, NHR; Y = PR2; Z = PR2, SR, S-) in a convergent manne r is described. The procedure is based on the aminolytic cleavage of f unctionalized oxetanes CH3C(CH2OCH2)CH2R 1 by primary or secondary ami nes, leading to functionalized amino alcohols CH3C(CH2NHR')(CH2OH)(CH2 R) or CH3C(CH2NR2')(CH2OH)(CH2R) 2. The appropriate activation of the R (e.g. OR) and OH groups present in 2 allows for substitution vs. SR or PR2 donor functions. Depending on the nature of the groups present in each reaction step, various protection and deprotection steps have to be taken in the course of this type of preparation of the tripod Li gands 3. By reaction with (CH3CN)(3)Mo(CO)(3), ligands 3 form Mo(CO)(4 ) derivatives 4 or Mo(CO)(3) derivatives 5, depending on the reaction conditions. In compounds 4, the Ligands are coordinated in a bidentate mode with the soft donor atoms (P, S) coordinated and the hard donor function playing the role of the dangling arm. In the trihapto bonding mode present in 5, all three donor functions, two soft (P, S) and one hard (NHR', NR2'), are coordinated. The two types of coordination com pounds may be interconverted: 4e (X = NMe2, Y = PPh2, Z = SiPr) with a non-coordinating CH2NMe2 group is transformed into 5e upon photolytic decarbonylation. Under 1 bar CO at 20 degrees C, 5c reverts to 4e. X- ray structure analysis of a series of com pounds of types 4 and 5 reve als characteristics of the relevant conformational patterns. All compo unds have been fully characterized by the standard analytical techniqu es (NMR, MS), as well as elemental analysis.