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Structural Variations and Chemical Bonding in Platinum Complexes of Group 14 Heavier Tetrylene Homologues (Germylene to Plumbylene)

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Structural Variations and Chemical Bonding in Platinum Complexes of Group 14 Heavier Tetrylene Homologues (Germylene to Plumbylene) Indian Journal of Chemistry Vol. 55A, March 2016, pp. 269-276 Structural variations and chemical bonding in platinum complexes of Group 14 heavier tetrylene homologues (germylene to plumbylene) Nguyen Thi Ai Nhung a, *, Huynh Thi Phuong Loan a, Duong Tuan Quang b, Tran Duc Sy b, c & Dang Tan Hiep d Email: [email protected] aDepartment of Chemistry, Hue University of Sciences−Hue University, Hue, Vietnam bDepartment of Chemistry, Hue University of Education−Hue University, Hue, Vietnam cDepartment of Chemistry, Quang Binh University, Dong Hoi, Vietnam dHCMC University of Food Industry, Ho Chi Minh, Vietnam Received 14 November 2015; revised and accepted 22 February 2016 The structures of Pt(II) complexes containing the heavier homologues of germylene, stannylene, and plumbylene [PtCl 2-{NHE Me }] (Pt-NHE) with E = Ge to Pb, in which the ligand {NHE Me } retains one lone pair at the E central atom, have been computed using density functional theory calculations at the BP86 level with def2-SVP, def2-TZVPP, and TZ2P+ basis sets. The bonding of the complexes has been analyzed by charge and energy decomposition analysis methods. The results of bonding analysis show that NHE Me ligands exhibit donor-acceptor bonds with the σ lone pair electrons of heavier NHE Me donated into the vacant orbital of the metal fragment, and the Pt-E bonds having PtCl 2←NHE Me strong σ-donation. The divalent heavier tetrylenes(II) have the same role as the divalent heavier tetrylones(0) character since the ligand can retain the two lone pairs at E atom. Currently experimental efforts are directed towards the synthesis of tetrylenes Pt(II) complexes from natural products. Hence, the results in this study will provide an insight into the properties and chemical bonding of complexes being synthesised. Keywords: Theoretical chemistry, Density functional calculations, Bonding analysis, Carbenes, Germylenes, Stannylenes, Plumbylenes, Platinum . The coordination chemistry of the heavier analogues analogues, germylene, stannylene, plumbylene 19-21 . of carbene-NHCs (silylenes, germylenes, and However, divalent plumbylene (NHPb) is more stable stannylenes) has attracted considerable attention than divalent carbon and has been considered as during the last 20 years 1-3, although less developed complexes featuring terminal ligands as reported than that of carbenes which was facilitated by the recently by Heitmann et al .22 , and Arp et al .23 From increasing propensity towards adopting divalent states the lighter to the heavier elements of Group 14, both as the group was descended 4. A large variety of the nucleophilicity and directionality of the lone pair N-heterocyclic silylenes (NHSi) 5, germylenes on the divalent atom decrease as there is increase in (NHGe) 6, and stannylenes (NHSn) derived from the s character and become more spherical 24 . Platinum different heterocycles which are stable at ambient complexes that carry NHCs ligands have been used temperature has been prepared 7. NHC complexes for the reductive cyclization of diynes and enynes 25 , including those of platinum, gold, silver, ruthenium, the catalytic diboration of unsaturated molecules 26 and nickel and copper have been used in catalytic the tandem hydroboration–cross coupling reaction 27 . reaction 8-11 , including C-C-coupling reactions 12 , olefin In addition, platinum complexes having antimicrobial metathesis 13 , hydroformylation 14 , polymerization activity have also been reported recently 28-30 . The reactions 15 and CH activation 16 . Many NHCs derived complexes of heavier analogues of carbene, i.e., from heterocycles are moisture stable 17 , generally less germylene, stannylene, and plumbylene, with toxic than those with similar donor characteristics platinum complexes have also been reported in the (phosphines and carbonyls) and less susceptible to recent past 4,19,23,24,31 . In view of the above, we have 8 dissociation . Electronically, the NHC ligand is studied the [(PtCl 2-{NHE Me }] (Pt-NHE) complexes considered to be a better σ donor, and a weaker π with E = Ge to Pb, for an insight into the nature of the 18 acceptor, than the phosphine ligand . A similar unusual bonding between PtCl 2 and heavier bonding situation has been suggested for the heavier tetrylenes. We have investigated the donor-acceptor 270 INDIAN J CHEM, SEC A, MARCH 2016 complexes shown in Scheme 1. To the best of our level using the NBO 3.1 program 38 . The Wiberg bond knowledge, the present work is the first detailed study orders, natural partial charges, and molecular orbitals of the structures and bonding of the complexes with orbital energies were analysed at the BP86/def2- [PtCl 2-{NHE Me }]. The electronic structure of the TZVPP//BP86/def2-SVP level using the natural bond molecules has also been analyzed by the charge and orbital (NBO 3.1 program) method available in energy decomposition methods. Gaussian 09. The parent compounds and free ligands were re-optimized for the energy decomposition Computational Methods analysis with the program package ADF 2013.01 39 The geometries of the molecules were calculated with BP86 in conjunction with a triple-zeta-quality without symmetry constraints using the Gaussian 09 32 basis set using un-contracted Slater-type orbitals optimizer together with Turbomole 7.0 33 energies and (STOs) augmented by two sets of polarization gradients at the BP86 34 /def2-SVP 35 level of theory. function with a frozen-core approximation for the For the heavier Group 14 atoms, Sn and Pb, and the core electrons 40 . An auxiliary set of s, p, d, f and g Pt element of PtCl 2 fragment, small-core quasi- STOs was used to fit the molecular densities and to relativistic effective core potentials (ECPs) were represent the Coulomb and exchange potentials used 36 . The RI approximation was used for all accurately in each SCF cycle 41 . Scalar relativistic structure optimizations by using the appropriate effects were incorporated by applying the zeroth- auxiliary basis sets. All structures presented in this order regular approximation (ZORA) 42 . A thorough study were optimized to the minima on the potential insight into the nature of chemical bonding and energy surface (PES). The nature of the stationary properties of complexes was obtained using the points on the PES was also confirmed as energy EDA-NOCV method 43 under the C1 symmetric minima by frequency calculations. The bond geometries (without symmetry) at the BP86/TZ2P+ dissociation energy (BDE), De (kcal/mol), was level of theory. calculated at BP86/def2-TZVPP 37 //BP86/def2-SVP Results and Discussion Structures and energies The optimized structures of complexes Pt-NHGe to Pt-NHPb are illustrated in Fig. 1 and the calculated geometry parameters of molecules are presented in Table 1. There are no experimental values available for these complexes. The theoretically predicted Pt-E bond lengths show the shortest value for Pt-NHGe (2.283 Å) which increases from 2.283 to 2.559 Å for Fig. 1 ‒ Optimized geometries of Pt-NHGe to Pt-NHPb complexes at the BP86/def2-SVP level. [Bond lengths are given in Å; angles in degrees]. NHUNG et al .: BONDING IN Pt COMPLEXES OF GROUP 14 HEAVIER TETRYLENE HOMOLOGUES 271 Pt-NHSn (2.559 Å), while the longest value is 2.636 Å homologues 48 . As mentioned above, of the for Pt-NHPb. The germylene complex [(Cy 3P) 2Pt- theoretically predicted Pt-Ge bond lengths, the 44 GeCl 2] has an experimental Pt-Ge bond length of shortest value is 2.283 Å for Pt-NHGe and the longest 2.397 Å. Note that the experimental results obtained value is 2.636 Å for Pt-NHPb. It may be noted that by X-ray structural analysis of [(PPh 3)2Pt stronger bonds for heavier complexes do not correlate (bisstannylene)] 45 give Pt-Sn bond lengths in the range with the bond dissociation energy and longer Pt-E of 2.5735 to 2.5868 Å which are quite similar to that in bonds do not mean that the bonds become weaker 48 . the stannylene complex studied herein. However, the Note that the trend of the theoretically predicted experimental Pt-Pb bond length (2.8558 Å) in complex PtCl 2-heavier tetrylenes BDEs in this study is 46 [Pt(NHPb)-(PPh 3)3] is much longer than the PtCl 2- opposite to that reported for the complexes of NHPb distance in the plumbylene complex Pt-NHPb. tetrylenes recently 47-50 . The BDEs of complexes DFT calculations show that in the equilibrium Pt-NHE (E = Ge to Pb) in this study follow structures of complexes all the heavier ligands NHE Me the same trend as the tetrylones E(0) investigated in are bonded in a tilted orientation relative to the metal an earlier study; [W(CO) 5-{Ge(PPh 3)2}] to 48 fragment PtCl 2 in Pt-NHE (Table 1) wherein the [W(CO) 5-{Pb(PPh 3)2}] (39.7 to 44.6 kcal/mol) , bending angle, α, is 138.9° for Pt-NHGe. Note that [W(CO) 4-{Ge(PPh 3)2}] to [W(CO) 4-{Pb(PPh 3)2}] 50 the Pt-NHSn and Pt-NHPb complexes exhibit a (48.3 to 50.0 kcal/mol) , wherein the ligand significantly different bonding mode of the ligand as {E(PPh 3)2} retains the two lone pairs at the compared with the germylene complex, and have E central atom i.e., tetrylones E(0). From this, it may be α = 90.9 ° and 88.9 °, respectively. Regarding the tilted noted that the platinum complexes with divalent heavier tetrylenes E(II) in this study have the same features as orientation between the ligands NHE Me and the metal the divalent heavier tetrylones E(0) in which the ligands fragment PtCl 2, the bending angle of the heavier may retain the two lone pairs at the E atom of NHE Me .
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