Synthesis and characterization of new pentamethylcyclopentadienyl iridium hydride complexes

Polyhydrides of Platinum Group Metals: Nonclassical Interactions and σ-Bond Activation Reactions

“…Reaction of this compound with LiEt 3 BH affords the mononuclear dihydride IrH 2 (η 5 -C 5 Me 5 )­(PMe 3 ) ( 847 ), which gives the trihydride [IrH 3 (η 5 -C 5 Me 5 )­(PMe 3 )]­BF 4 ( 848 ) by protonation with HBF 4 ·OEt 2 (Scheme ). Similarly, the protonation of the dihydrides IrH 2 (η 5 -C 5 Me 5 )­(PR 3 ) (PR 3 = P i Pr 3 ( 849 ), PCy 3 ( 850 ), PPh 3 ( 851 ), PPh 2 Me ( 852 )) and IrH 2 (η 5 -C 5 H 5 )­(ER 3 ) (ER 3 = PMe 3 ( 853 ), P i Pr 3 ( 854 ), PCy 3 ( 855 ), PPh 3 ( 856 ), AsPh 3 ( 857 )) generates the corresponding trihydrides [IrH 3 (η 5 -C 5 Me 5 )­(PR 3 )]­BF 4 (PR 3 = P i Pr 3 ( 858 ), PCy 3 ( 859 ), PPh 3 ( 860 ), PPh 2 Me ( 861 )) and [IrH 3 (η 5 -C 5 H 5 )­(ER 3 )]­BF 4 (ER 3 = PMe 3 ( 862 ), P i Pr 3 ( 863 ), PCy 3 ( 864 ), PPh 3 ( 865 ), AsPh 3 ( 866 )), according to Scheme . The hydride ligands of these trihydride derivatives undergo thermally activated position exchange.…”

Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp3)–Oxygen Bond versus Aminolysis

“…31 P{ 1 H} NMR (CD 2 Cl 2 ): δ −12.08 (s, P Ph 2 CH 3 ) ppm. The nature of 8 was confirmed by comparing its NMR data with those of the [IrCp*Cl(CO)(PPh 2 Me)]BPh 4 complex recently reported and after a metathesis reaction of 8 with an excess of NaBPh 4 in methanol. 13 C{ 1 H} NMR (CD 2 Cl 2 ) (not previously reported): δ 166.1 (d, 2 J C–P = 14.3 Hz, C O); 132.6–133.3 (C P Ph 2 Me); 129.4–129.8 (C P Ph 2 Me); 129.0 (d, 1 J C–P = 61.7 Hz, C ipso ); 127.6 (d, 1 J C–P = 61.8 Hz, C ipso ); 105.6 (s, C 5 (CH 3 ) 5 ); 15.1 (d, 1 J C–P = 42.6 Hz, PPh 2 C H 3 ); 9.4 (s, C 5 ( C H 3 ) 5 ) ppm.…”

“…The hydroxycarbene 7 was unambiguously characterized by NMR spectroscopy ({ 1 H, 13 C} HMBC, { 1 H, 13 C} HSQC, 13 C{ 1 H}) and confirmed by refluxing complex 2 with water and 1,1-diphenyl-2-propyn-1-ol for 30 min . When the reaction mixture of 5 and trifluoromethanesulfonic acid was set aside for 2 h, the carbonyl complex 8 and 1,1-diphenylethene were formed. Moreover, when the same reaction was performed with 4 equiv of acid and set aside overnight, the 1,1-diphenylethene transformed into 3-methyl-1,1,3-triphenylindane .…”