The synthesis of RuCp(PPh2NHR)2Cl (1a,b; R = Ph, n-Pr) and RuTp(PPh2NHR)2Cl (2a,b) is reported. Chloride abstraction from 1a with AgCF3SO3 affords RuCp(PPh2NHPh)2(η1-OSO2CF3) (3), whereas when AgSbF6 is used instead [RuCp(κ2(P,P)-PPh2NHC6H4PPh2)(NH2Ph)]+ (4) is formed. In the course of this reaction the P−N bond of one PPh2NHPh ligand is cleaved while a new P−C bond is formed, with concomitant formation of an aniline ligand. In the presence of Ag+ (CF3SO3 - or SbF6 -) complexes 1 and 2 react with terminal alkynes HC⋮CR‘ (R‘ = Ph, p-C6H4Me, n-Bu) and propargylic alcohols to give novel azaphosphacarbene complexes of the types [RuCp(κ2(C,P)C(CH2R‘)N(R)PPh2)(κ1(P)-PPh2NHR)]+ (5a−c, 6a−c), [RuTp(κ2(C,P)C(CH2R‘)N(R)PPh2)(κ1(P)-PPh2NHR)]+ (14a,b, 15a−c), [RuCp(κ2(C,P)C(CHCPh2)N(Prn)PPh2)(κ1(P)-PPh2NHPrn)]+ (12), and [RuTp(κ2(C,P)C(CHCPh2)N(Prn)PPh2)(κ1(P)-PPh2NHPrn)]+ (17). These reactions proceed via vinylidene and allenylidene intermediates, respectively, which could be isolated in some cases:  viz. [CpRu(PPh2NHPh)2(CCCPh2)]+ (11) and [RuTp(PPh2NHR)2(CCCPh2)]+ (16a,b). Furthermore, complexes 1a,b react with 3-butyn-1-ol to yield the oxacyclopentylidene complexes [CpRu(PPh2NHR)2(C4H6O)]+ (7a,b). In sharp contrast to 6a−c (R = n-Bu), 5a−c (R = Ph) turned out to be quite sensitive toward traces of water, leading eventually to the formation of the aminocarbene complexes [RuCp(C(CH2R)NHPh)(PPh2NHPh)(κ1(P)-PPh2OH)]+ (8a,b) featuring a κ1(P)-coordinated PPh2OH ligand. This ligand could be easily deprotonated to yield the neutral complex RuCp(C(CH2Ph)NHR)(PPh2NHPh)(κ1(P)-OPPh2) (10a,b). The formation of these complexes is reversible. Finally, representative structures have been determined by X-ray crystallography.

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This is a continuation of our work on the reactions of [RuCp(PR 3 )(CH 3 CN) 2 ]PF 6 with terminal alkynes and diynes. Here now we use, instead of PR 3 , the phosphino-amine ligand PPh 2 NHPh. The reaction pattern is found to be similar except that the N-H bond of the phosphine ligand is activated and not a C-H bond as before. Thus the reaction of [RuCp(PPh 2 NHPh)(CH 3 -CN) 2 ]PF 6 with HCtCR (R ) Ph, n-Bu, CH 2 Ph), 1,6heptadiyne, and 1,7-octadiyne results in the formation of the η 4 and [RuCp(η 4 -C 4 H 3 (CH 2 ) 4 -PPh 2 -κ 1 -(N)-NPh)]PF 6 in good yields.