The chromium(III) catalysts based on tridentate silicon-bridged tris(diphenylphosphine) ligands of the form RSi(CH2PPh2)(3) (L-1: R = Me; L-2: R = Cy; L-3: R = Ph) were investigated for selective ethylene tri-/ tetramerization. The steric and electronic properties of the substituents attached to the silicon moiety have been observed to have a great impact on the catalytic performance of these catalysts. Singlecrystal analysis, high-resolution mass spectrometry (HR-MS), and elemental analysis revealed that these complexes may adopt mononuclear tridentate coordination mode (k(3)-P, P, P) with Cr center. However, one of the phosphorus atoms in these complexes may act as a hemilabile donor and presumably loses its coordination with chromium in the presence of a competent donor which consequently transformed the tridentate complexes to bidentate (k(2)-P, P) coordination mode. Backbone modification of L1 of the precatalyst 1 via successive abstraction of methylene spacers may offer MeSi(CH2)(n)(PPh2)(3) (L-4: n = 2; L-5: n = 1; L-6: n = 0) type chromium(III) complexes. Ethylene oligomerization of these systems suggested that the methylene spacers may effectively tune the complex structure and catalytic performance. Precatalyst 1 and 4 respectively based on L-1 and L-4 deliver 70% C-8 selectivity in the liquid oligomeric fraction and considerable activity under experimental conditions. DFT investigations based on catalyst 4 revealed that the catalyst may simultaneously facilitate the single and double coordination pathways for C-8 formation, however, the single coordination pathway is thermodynamically more favorable for this system. (C) 2020 Published by Elsevier Inc.