Gold(I) complexes of sterically demanding phosphines derived from 2,6-dibenzhydryl-4-methylphenyl core viz: 2,6-dibenzhydryl-N,N-bis((diphenylphosphane)-methyl)-4-methylaniline (1), (2,6-dibenzhydryl-4-methylphenyl)-diphenylphosphane (2), N-(2,6-dibenzhydryl-4-methylphenyl)-1,1-diphenylphosphanamine (3), and (2,6-dibenzhydryl-4-methylphenoxy)-diphenylphosphane (4) are described. The reaction of 1 with 2 equiv of [AuCl(SMe2)] in dichloromethane yielded [{AuCl}(2){Ar*N(CH2PPh2)(2)}] (5), which on further treatment with 2 equiv of AgSbF6 and 1 equiv of 1 produced 12-membered dimeric complex [Au-2{mu-(Ar*N(CH2PPh2)(2))(2)}][(SbF6)(2)] (6). A similar reaction of 5 with AgSbF6 in CH3CN afforded [{Au-(NCCH3)}(2) {Ar*N(CH2PPh2)(2)}][(SbF6)(2)] (7). Equimolar reac- tions of bulky phosphines 2, 3, and 4 with [AuCI(SMe2)] resulted in [AuCl(PPh2Ar*)] (8), [AuCl(PPh2NHAr*)] (9), and [AuCl(PPh2OAr*)] (10). Complexes 9 and 10 on treatment with AgSbF6 in CH3CN produced the cationic complexes [Au(NCCH3)(PPh2NHAr*)][(SbF6)] (11) and [Au(NCCH3)(PPh2OAr*)][(SbF6)] (12), respectively. The molecular structure of complex 6 revealed the presence of a strong intramolecular aurophilic interaction with a Au center dot center dot center dot Au distance of 2.9720(4) angstrom. Careful analysis of molecular structure of 5 revealed the presence of rare Au center dot center dot center dot H-C (sp(3)) interactions between the gold(I) atom and one of the methylene protons of -NCH2PPh2 groups. The solution H-1 NMR signals of the methylene protons of 5 showed a considerable downfield shift (similar to 1 ppm) compared to that of the free ligand indicating their interactions (Au center dot center dot center dot H) with the Au atom. Complexes 8 and 10 also showed Au center dot center dot center dot H interactions in their molecular structures. The existence of the Au center dot center dot center dot H interaction was studied by variable temperature H-1 NMR data in the case of complex 5 and further evinced by the QTAIM analysis in complexes 5, 8, and 10.