A series of bis(σ)-borane complexes of Group 6 transition metals were prepared by direct dihydroborane coordination to the metal center. Reaction of [M(CO)3 (PCy3 )2 ] and two dihydroboranes [DurBH2 ] and [(Me3 Si)2 NBH2 ] (Dur=2,3,5,6-Me4 C6 H) yielded bis(σ)-borane complexes fac-[M(CO)3 (PCy3 ){η2 -(H2 BR)}] (R=Dur; 1: M=Cr, 2: M=W; R=N(SiMe3 )2 ; 3: M=Cr, 4: M=W). In the case of molybdenum, we have isolated an arene complex (5) with [DurBH2 ] in which the Dur group acts as a η6 -bound ligand, and with [(Me3 Si)2 NBH2 ] a similar bis(σ)-borane complex was isolated, cis,trans-[Mo(CO)2 (PCy3 )2 {η2 -(H2 BN(SiMe3 )2 }] (6), with a different pattern of auxiliary ligands. The complexes were investigated by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and computational methods. Quantum theory of atoms in molecules (QTAIM) calculations demonstrated that the borane complexes may be described as pure bis(σ)-borane complexes rather than elongated or stretched examples given that the calculations do not show the presence of a ring-critical point (RCP) at the ring formed by the interactions of the B-H with metal center.