Structure and Bonding Energy Analysis of Cobalt, Rhodium, and Iridium Borylene Complexes [(η⁵-C₅H₅)(CO)M(BNX₂] (X = Me, SiH₃, SiMe₃) and [(η⁵-C₅H₅)(PMe₃)M{BN(SiH₃)₂}] (M = Co, Rh, Ir)

Abstract

Geometry, electronic structure, and bonding analysis of the terminal neutral borylene complexes of cobalt, rhodium, and iridium [(η 5 -C 5 H 5 )(CO)M(BNMe, and [(η 5 -C 5 H 5 )(PMe 3 )M{BN(SiH 3 ) 2 }] (X, M = Co, XI, M = Rh, XII, M = Ir) were investigated at the BP86 level of theory. The calculated geometry parameters of iridium borylene complex [(η 5 -C 5 H 5 )(CO)Ir{BN(SiMe 3 ) 2 }] are in excellent agreement with their available experimental values. Pauling bond order of the optimized structures of I-XII shows that the M-B bonds in these complexes are nearly MdB double bonds, which is also supported by the performed energy decomposition analysis. The orbital interactions between the metal and boron arise mainly from MrBNX 2 σ-donation. In all complexes, the π-bonding contribution is smaller (26.2-37.0% of total orbital contributions) and increases via M = Rh < Co < Ir. In all the complexes, the M-B π-bond orbitals are highly polarized toward the metal atom. Thus, in the BNX 2 ligands, boron dominantly behaves as a σ-donor. The calculated MdBNX 2 interaction energy increases in all four sets of complexes in the order Co e Rh < Ir. The contributions of the electrostatic interactions, ΔE elstat , are significantly larger in all studied borylene complexes than the covalent bonding ΔE orb : the MdBNX 2 bonding in the neutral borylene complexes has a greater degree of ionic character (61.2-68.5%). The iridium complexes possess the highest orbital interactions, ΔE orb , and electrostatic interactions, ΔE elstat .

Towards Homoleptic Borylene Complexes: Incorporation of Two Borylene Ligands into a Mononuclear Iridium Species

“…By contrast, the BÀN bonds of 1.398(3) and 1.393(3) in the former are elongated by approximately the same amount compared to the BÀN bond in 3 (1.365(4) ). In line with previous theoretical results by Pandey and Musaev for compounds [(h 5 -C 5 H 5 )(OC)Ir = BN-(SiR 3 ) 2 ] (3': R = H; 3'': R = Me), [19] 3 and 5 can be considered typical examples of terminal aminoborylene complexes.…”

Bonding in Endohedral Metallofullerenes as Studied by Quantum Theory of Atoms in Molecules

“…Dagegen sind die B‐N‐Bindungen von 1.398(3) und 1.393(3) Å jedoch um etwa denselben Betrag aufgeweitet wie der B‐N‐Abstand in 3 (1.365(4) Å). In Übereinstimmung mit früheren theoretischen Untersuchungen von Pandey und Musaev an den Verbindungen [(η 5 ‐C 5 H 5 )(OC)IrBN(SiR 3 ) 2 ] ( 3′ : R=H; 3′′ : R=Me)19 können 3 und 5 als typische Beispiele für terminale Aminoborylenkomplexe betrachtet werden 11b. 15, 20 Ein ähnlicher Trend kann für die C‐O‐Abstände in den Carbonylkomplexen 1 14b und 3 nach CO‐Borylen‐Austausch beobachtet werden (Tabelle 1).…”

DFT Study on Alkyl‐ and Haloborylene Complexes of Manganese and Rhenium: Structure and Bonding Energy Analysis in [(η5‐C5H5)(CO)2M(BR)] and [(η5‐C5H5)(CO)2M(BX)] (M = Mn, Re; R = Me, Et, iPr, tBu; X = F, Cl, Br, I)

“…Previously, the BLYP/LANL2DZ and B3LYP/LANL2DZ approaches have been applied to study thegeometry and electronic structure of terminal cationicborylene complexes [(η 5 ‐C 5 H 5 )(CO) 2 Fe{B(η 5 ‐C 5 Me 5 )}] + ,[(η 5 ‐C 5 H 5 )(CO) 2 Fe(BMes)] + , [(η 5 ‐C 5 H 5 )(CO) 2 Fe(BNMe 2 )] + and [(η 5 ‐C 5 H 5 )(CO) 2 Ru(BNMe 2 )] + 16,20,21,45. Structure and bonding energy analysis of borylene complexes of iron, ruthenium and osmium46 and of cobalt, rhodium and iridium47 have been studied in detail. For our model systems, we have investigated the degree of ionic and covalent character of the M=B bonds as well as the M←B σ bonding and the M → B π back bonding contributions to the M=B bonds (see Figure 1 for schematic presentation of M=BR and M=BX bonds).…”