(M = Mn, Fe, & Co) Hydrogen Bond - ACS Publications - American

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Nature and Strength of M-H•••S and M-H•••Se (M=Mn, Fe & Co) Hydrogen Bond Dipak Kumar Sahoo, Subhrakant Jena, Juhi Dutta, Abhijit Rana, and Himansu S. Biswal J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.8b12003 • Publication Date (Web): 25 Feb 2019 Downloaded from http://pubs.acs.org on March 2, 2019

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The Journal of Physical Chemistry

Nature and Strength of M-H•••S and M-H•••Se (M=Mn, Fe & Co) Hydrogen Bond Dipak Kumar Sahoo1,2, Subhrakant Jena1,2, Juhi Dutta1,2, Abhijit Rana1,2, and Himansu S. Biswal1,2* 1

School of Chemical Sciences, National Institute of Science Education and Research (NISER),

PO- Bhimpur-Padanpur, Via-Jatni, District- Khurda, PIN - 752050, Bhubaneswar, India 2

Homi Bhabha National Institute, Training School Complex, Anushakti Nagar, Mumbai 400094,

India * Corresponding Author’s E-mail: [email protected], Phone No: - +91-674-2494 185/186

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ABSTRACT The significance of dispersion contribution in the formation of strong hydrogen bonds (H-bonds) can no more be ignored. It has been illustrated that less electronegative and electropositive Hbond acceptors such as S, Se and Te are also capable of forming strong N-H•••Y H-bonds, mostly due to the high polarizabilities of H-bond acceptor atoms. Herein, for the first time, we report the evidences of formation non-conventional M-H•••Y H-bonds between metal hydrides (M-H, M=Mn, Fe, Co) and chalcogen H-bond acceptors (Y=O, S or Se). The nature and the strength of unusual M-H•••Y H-bonding were revealed by several quantum chemical calculations and H-bond descriptors. The structural parameters, electron density topology, donoracceptor natural bond orbital (NBO) energies and spectroscopic observables such as M-H stretching frequencies and 1H chemical shifts are well correlated to manifest the existence and strength of M-H•••Y H-bonding. The M-H•••Y H-bonds are dispersive in nature and the computed H-bond energies are found to be in the range of ~5 to 30 kJ/mol, that can be compared to those of the conventional H-bonds such as O-H•••O, N-H•••O and N-H•••O=C H-bonds etc.


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INTRODUCTION Hydrogen Bond (H-bond) has been one of the most familiar non-covalent interaction since its inception by Moore and Winmill in 1912.1 Its importance can profoundly be noticed in many physical, chemical and biochemical processes.2-9 Over the years a steady evolution in the hydrogen bond concept has been perceived not only through elucidation of its nature but also due to the extension of the range of H-bonding partners. It is now no longer confined to conventional X-H•••Y type interactions where X-H indicates the proton donor and Y as proton acceptor and both X and Y are electronegative atoms. Many nonconventional H-bonds such as C-H•••Y, XH•••C, X-H•••π or even C-H•••C H-bonds have emerged in the recent time.10-16 Recently the advent of homopolar dihydrogen bond such as N-H•••H-N, C-H•••H-C or C-H•••H-N interactions seem to enumerate another weak H-bond.9 The H-bond can now be extended to S, Se and Te centers H-bonds.4, 7-8 The strengths of these H-bonds are also comparable to those of the conventional H-bonds. However, the IUPAC definition of H-bond underlines: “The hydrogen bond is an attractive interaction between a hydrogen atom from a molecule or a molecular fragment X–H in which X is more electronegative than H....”.17 It is true for most of the H-bonds that X is more electronegative than H, but it is not universal and may not be valid for all the Hbonds. From chemical intuition it is always expected that O due to its more electronegativity than S and Se, can form strong H-bonds. It is reasonable when electrostatics plays major role and dispersive interaction is a minor contributor. But when dispersion and polarization are dominant, then there are chances that S and Se might surpass their O counterpart in H-bond formation due to higher polarizability of S and Se atoms than O atom. The significant role of polarizability and dispersion has been evoked in explaining higher or equivalent strength of S/Se/Te centered Hbonds compared to O centered H-bonds in small organic molecules as well as proteins and amino acids.4, 8 McDowell et al. in their recent published work emphasized the dominance of dispersion and polarization while explaining the effect of anions on clusters of chalcogen containing (CH3)2X (X=O, S, Se).18 In addition, Niemann et al. in their current research have accentuated that dispersion forces enhance the cationic cluster formation in cooperative hydrogen bonding and at the same time compensate the electrostatic repulsion of positive charges.19 Most of the works on S or Se centered H-bonds include O-H•••S, O-H•••Se, N-H•••S and N-H•••Se Hbonds.4,

8, 17-18

Herein, we for the first time report M-H•••S and M-H•••Se H-bonds between

neutral transition metal carbonyl hydrides (M(CO)yHx: x=1 for M=Mn, Co and 2 for M=Fe; and



y=4 for M=Fe, Co and 5 for M=Mn) and sulfur and selenium as H-bond acceptors. These are represented as M-H•••Y (M=Mn, Fe & Co and Y=O, S & Se) where M is less electronegative than H i.e. the electro negativities of Mn, Fe, Co and H atoms in Pauling scale are 1.55, 1.83, 1.88, and 2.2 respectively.20 In the past decade, transition metal hydrides have been shown to play an important role in chemistry, catalysis and biochemical processes.3, 21-27 Depending on the substrate, the reactions of transition metal hydrides may involve H+ donation (acidic) or H- donation (basic) in proton transfer reactions. The reactivity of transition metal hydrides dictated that the proton transfer occurs from X-H acid to transition metal hydride through a dihydrogen bonded intermediate complex M-Hδ-•••Hδ+X.24-25,

28

Levina et al.26 found emergence of the H-bonded complex

between neutral transition metal hydride and a neutral base (B), M-Hδ+•••B where M= Mo, W & B=organic bases. It is now well established regarding the reactivity of neutral transition metal hydrides where they act as the source of hydrogen atom H., hydride ion H- or proton H+.21, 27 Shubina and co-workers in their study found both spectroscopic and theoretical evidences for the formation of intermolecular hydrogen bond with neutral hydride complex CpM-(CO)3H (M = Mo, W) as an acid with bases like pyridine and phosphine oxide.29 The electronegativities of Mo and W are 2.16 and 2.36, respectively that are close or marginally higher than that of H; hence Mo-H•••Y and W-H•••Y H-bonds still adhere to the IUPAC definition of H-bond. To the best of our knowledge there are no reports on M-H•••Y H-bonds where M is a first row transition metal with smaller electronegativity than H. In this work, extensive quantum chemical calculations have been used to determine the nature and strength of unusual intermolecular H-bonds between first row transition metal carbonyl hydrides and simple bases such as dimethylether (DME), dimethylsulfide (DMS) and dimethylselenide (DMSe). The evidences for the presence of MH•••Y H-bonds are revealed through extensive structural analysis and quantum theory of atoms in molecules (QTAIM) criteria proposed by Koch and Popelier30 followed by Localized Molecular Orbital Energy Decomposition Analysis (LMOEDA)31-32 and Natural Bond Orbital (NBO) analyses.33-34 Spectroscopic properties such as IR stretching frequency shifts (ΔυM-H) and 1

H downfield NMR chemical shifts were also calculated to characterize the hydrogen bonds and

correlate with the H-bond energy (EH), H-bond distance (dH•••Y), NBO and AIM interaction energies.


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Figure1. Metal carbonyl hydrides as H-bond donors: Mn(CO)5H, Fe(CO)4H2, Co(CO)4H; H-bond acceptors: H2S, DMS, H2Se, DMSe and DME; Optimized structures of H-bonded complexes of donors and acceptors at RI-B97D/def2-TZVPPlevel. The bond distances are given in pm.

COMPUTATIONAL METHODS Geometry optimization and frequency calculations of all the monomers and complexes were carried out with Turbomole quantum chemistry package35 at RI-B97D/def2-TZVPP level. Absence of imaginary frequency in all the optimized structures confirmed that the optimized structures are the minimum energy structures. Binding energies of the complexes were calculated by RI-B97D/def2-TZVPP level of theory with basis set superposition error (BSSE) correction. Topological parameters such as electron density(ρ), Laplacian of electron density(𝛻𝛻2ρ), local kinetic energy density (Gc) and local potentials energy density (Vc) at the bond critical points (BCPs) were analyzed by Bader’s “atoms in molecules” (AIM) theory.36-37 The change in bonded hydrogen atom charge (ΔqH); energy (ΔEH); dipolar polarization (Δ|MH|); volume (ΔVH); population (ΔNH); and mutual penetration (ΔrH) of metal hydrides proposed by Koch and Popelier were also evaluated. Donor acceptor orbital interaction energies were estimated with



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natural bond orbital (NBO) analysis.33-34 Both NBO donor-acceptor interaction energies and wave functions used in QTAIM were obtained at the MP2 and B97D functional with aug-ccpVDZ basis set using Gaussian 09 program package.38 The NBO and AIM parameters obtained at the above mentioned two levels of theories follow the same trend (see Tables S1, S5 and S6). However, we used MP2/ aug-cc-pVDZ level of theory throughout the manuscript as postHartree–Fock wave functions are better to predict AIM topology and NBO second order perturbation energies. Energy decomposition analysis (EDA) was carried with Localized molecular orbital EDA (LMOEDA) scheme as implemented in quantum chemistry program package Gamess31-32 at MP2/aug-cc-pVDZ level of theory. To better understand the non-covalent interactions in H-bond complexes, we used NCIPLOT software39 for plotting a graph between reduced density gradient (RDG) and the sign of second Eigen value of the electron density hessian matrix times the electron density i.e. sign(λ2)ρ(r). The wave functions obtained at MP2/aug-cc-pVDZ were used to generate the density cube files and gradient cube files using NCIPLOT.32 Visual molecular dynamics (VMD) software40 was used to visualize the isosurfaces. Molecular electrostatic potential (MESP) surfaces were plotted with Gauss View. 1H NMR chemical shifts of metal hydrides were obtained at B97D/def2-TZVPP level while taking tetra methyl silane (TMS) as the reference.

RESULTS and DISCUSSION Binding energies and geometries To confirm the existences of H-bonds in M-H•••Y (M=Mn, Fe, Co & Y=O, S, Se), we analyzed geometrical parameters of monomers and complexes optimized at RI-B97D/def2TZVPP. This level of theory has already been benchmarked with the experimental spectroscopic parameters of several metal hydrides as well as nonconventional H-bond complexes such as amide-NH•••S and amide-NH•••Se H-bond dimers.4,

7-9, 41-45

. Further, we have also bench

marked ab initio and several density functionals on the experimental M-H stretching frequency data of transition metal hydrides and found that B97D is the best choice for computational studies (see Table S3).41 First we explored the non-conventional M-H•••Y H-bonds involving transition metal hydrides as H-bond donor and H2O, H2S, H2Se as H-bond acceptors and then we proceeded to stronger bases such as DME, DMS and DMSe as H-bond acceptors.


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Table 1. Hydrogen bond distance (dH•••Y), difference between the sum of van der Walls radii of M & H and dH•••Y (ΔdH•••Y), M-H bond distance (dM-H), difference between the M-H bond distances in the complexes and the respective monomers (ΔdM-H), H-bond angle (∠M-H•••Y), the BSSE corrected binding energies of H-bond complexes with dispersion (ΔEBSSE)disp and the BSSE corrected binding energies of H-bond complexes without dispersion ΔEBSSE.

(pm)

(ΔEBSSE)disp (kJ/mol)

ΔEBSSE (kJ/mol)

ΔEdisp (kJ/mol)

-3.96

-0.15

-4.67

4.43

-9.10

1.74

-0.04

-6.02

4.63

-10.65

269.58 162.9 30.42 0.47 -11.48 Co-H···SH2 271.99 171.0 28.01 0.59 -14.64 Mn-H···SMe2 253.14 166.9 46.86 1.51 -17.64 Fe-H···SMe2 220.16 175.3 79.84 4.81 -27.72 Co-H···SMe2 302.31 180.0 7.69 -0.58 -4.57 Mn-H···SeH2 300.42 151.8 9.58 0.01 -7.23 Fe-H···SeH2 272.18 164.2 37.82 0.71 -12.54 Co-H···SeH2 279.14 172.9 30.86 0.83 -15.69 Mn-H···SeMe2 256.38 168.7 53.62 1.95 -19.59 Fe-H···SeMe2 231.27 175.3 78.73 4.96 -29.28 Co-H···SeMe2 c 233.10 162.9 38.9 0.291 -9.47 Co-H···OH2 247.16 170.2 24.84 -0.40 -9.57 Mn-H···OMe2 232.96 163.3 39.04 0.01 -11.87 Fe-H···OMe2 208.86 174.0 63.14 0.81 -17.93 Co-H···OMe2 vdw vdw a: ΔdH•••Y = (r H + r Y) - dH•••Y b: ΔdM-H = dM-H(Monomer) ̶ dM-H(Complex) c: Mn-H•••OH2 and Fe-H•••OH2 H-bond complexes were not found; see text.

3.34 12.87 12.44 7.46 3.11 5.47 4.28 12.68 12.79 6.75 1.22 11.48 10.62 6.68

-14.82 -27.51 -30.08 -35.18 -7.69 -12.70 -16.82 -28.37 -32.38 -36.03 -10.69 -21.05 -22.49 -24.62

Species Mn-H···SH2 Fe-H···SH2

dH•••Y (pm)

∠M-H•••Y (°)

ΔdH•••Ya (pm)

ΔdM-Hb

303.96

171.8

298.26

150.6

The selected geometrical parameters along with counterpoise-corrected binding energies of all the complexes are given in Table 1. The H-bond donors (metal hydrides), acceptors (H2S, H2Se, DME, DMS and DMSe) and their optimized complexes are shown in Figure 1. We couldn’t find Mn-H•••OH2 and Fe-H•••OH2 H-Bond complexes since H2O approaches to carbonyl group of metal hydrides in their optimized structures forming C=O•••H2O H-bonds. Hence, for better comparisons in most cases of this work, we have focused only on M-H•••Y H-bonds involving DME, DMS and DMSe as acceptors. The BSSE corrected binding energies of all the complexes (Table 1) range between -4 and -30 kJ/mol which are comparable to those of water dimers and



many non-covalently bonded complexes.4, 46-49 In all the complexes, the intermolecular distances between H atom and acceptor atoms (O, S, Se) i.e. dH•••Y lie within the sum of van der Waals radii of H and Y atoms except Mn-H•••SH2. The ΔdH•••Y values are larger in Co complexes indicating stronger H-bonding interactions in Co complexes compared to the corresponding Mn and Fe complexes which are in agreement with the binding energies. The formation of linear MH•••Y H-bonds were observed with the H-bond angles ∠M-H•••Y falling in the range of ~150-

180o.50 Elongation of M-H bond was observed for all cases except in Mn-H•••OMe2 and Mn-

H•••SeH2 where a small Mn-H bond contraction was observed. The largest M-H bond elongation is 4.96 pm for Co-H•••Se while smallest elongation is 0.01 pm for Fe-H•••O interaction. As a thumb rule, more is the elongation of M-H bond, stronger is the M-H•••Y H-bonds. It can be inferred that S and Se of DMS and DMSe are capable of forming stronger H-bonds with transition metal hydrides than O of DME. The dispersion energy contributions (ΔEdisp) for all the complexes were evaluated from the difference of BSSE corrected interaction energies with and without Grimme’s long range dispersion correction (DFT-D3)51 i.e. difference between (ΔEBSSE)disp and (ΔEBSSE) as shown in Table 1. It is observed that dispersion contribution follows the order Se > S > O; e.g. the dispersion energy contributions to the total binding energy for CoH···SeMe2 and Co-H···SMe2 are 36.03 kJ/mol and 35.18 kJ/mol, respectively whereas it is 24.62 kJ/mol for Co-H···OMe2 complex. This can be attributed to the higher polarizability of S and Se atoms than O atom as illustrated for N-H•••S and N-H•••Se H-bonds in biomolecules.4-5, 7-8, 42 By using molecular polarizability partitioning method as described by Truhlar and coauthors52, the spherically averaged static polarizability of Se, S and O atoms in DMSe, DMS and DME were found to be 14.6, 11.87 and 3.48 au, respectively at M06/aug-cc-pVDZ level. It is further supported by a recent publication by McDowell18 that demonstrated the dominance of polarization over electrostatic dipole-dipole interaction.


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Figure 2. Potential energy (PE) curves of M-H•••Y H-Bond dimers: (a), (c) Mn(CO)5H•••DMS, Fe(CO)4H2•••DMS, Co(CO)4H•••DMS representing M-H•••S H-Bonds; (b), (d) Fe(CO)5H•••DME, Fe(CO)5H•••DMS,

Fe(CO)5H•••DMSe

representing

Fe-H•••O,

Fe-H•••S,

Fe-H•••Se

H-Bonds,

respectively. Left part of the plot (a,b) represents PE curves without dispersion correction i.e. RIB97D/def2-TZVPP without Grimme’s long range dispersion correction and right part of the plot (c,d) represents PE curves with dispersion i.e RI-B97D /def2-TZVPP with Grimme’s long range dispersion

correction. BSSE is added to the dimerization energy.



To check the possible contribution of long range dispersion in stabilizing M-H•••Y H-bond complexes, we also performed relaxed potential energy scan by varying H•••Y distances at RIB97D/def2-TZVPP level sans Grimme’s long range dispersion correction. We kept H•••Y distance fixed and relaxed all other geometrical parameters during the optimization. Figure 2a,b show a plot of BSSE corrected binding (or dimerisation) energy (ΔE) versus the H•••Y distance. We did not find a minimum in the potential energy (PE) curve i.e. PE curve is dissociative in nature without the inclusion of long range dispersion correction. At shorter distances it is repulsive and at longer distances it approaches the dimer dissociation asymptote. While performing the same with Grimme’s long range dispersion correction (DFT-D3) i.e. at RIB97D/def2-TZVPP, we obtained nice minima in the PE curve (Figure 2c-d). The energy minima obtained for Co complexes are deeper compared to Mn and Fe complexes (Figure 2c) in accordance with the formation of stronger hydrogen bond with Co-H. We obtained similar PE curves for M-H•••O and M-H•••Se complexes (Figure S1). Thus dispersion correction (DFT-D3) should be included in the study of unusual M-H•••Y H-Bonds systems. Electron density topology analysis Inspection of electron density and its Laplacian through atoms in molecules (AIM) not only enables to discern non covalent bonds but also provide an alternative way to estimate their strength. We characterized the nature of M-H•••Y H-Bonds based on the Bader’s theory36-37 of AIM electron density topology at the bond critical points (BCP). The molecular graph of Fe(CO)4H2•••DMS is shown in Figure 3(a) as a representative example and molecular graphs of all other complexes with DME, DMS and DMSe acceptors are shown in Figure S2-S4(a-c). A BCP was located along the H-bond vector; depicted as small red colored dot between two interacting atoms. AIM topological parameters for all the complexes are provided in Table 2. The covalent or non-covalent nature of M-H•••Y H-bonds can be predicted from the electron density topology at BCP. For example the value of –Gc/Vc ratio can be used (Gc: kinetic energy density, Vc: potential energy density) to predict the nature of interaction.53 If the ratio lies within 0.5 to 1, the interaction is non-covalent where less than 0.5 values indicate covalent interaction. The –Gc/Vc values of M-H•••Y presented in Table S1 are close to 1, confirming the M-H•••Y interactions are non-covalent and attractive in nature. It is well established that parameters like electron density (ρc), its Laplacian ∇2(ρc) and the H-bond energies (EH•••Y) calculated from AIM ACS Paragon Plus Environment

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theory at BCP correlate with the H-bond distances.54 Figure 3e and 3f show linear correlation between ρc and EH•••Y with dH•••Y. For a particular Y, both ρc and EH•••Y vary linearly with H•••Y distance (dH•••Y) for M-H•••Y H-bond systems with DME, DMS and DMSe as H-bond acceptors. All these electron density analysises suggest that M-H•••Y H-bonds are possible and their strengths are comparable to those of conventional H-bonds. Table 2. Topological parameters like electron density (ρH), Laplacian of electron density (∇2ρH), change in bonded hydrogen charge (ΔqH), energy (ΔEH), dipolar polarization (Δ|MH|), volume (ΔVH), population (ΔNH), and mutual penetration (ΔrH) of H-bond complexes of metal hydrides and several H-bond acceptors (H2O, H2S, H2Se, DME, DMS and DMSe). All the values are in atomic units. complexes Mn-H···SH2 Fe-H···SH2 Co-H···SH2 Mn-H···SMe2 Fe-H···SMe2 Co-H···SMe2 Mn-H···SeH2 Fe-H···SeH2 Co-H···SeH2 Mn-H···SeMe2 Fe-H···SeMe2 Co-H···SeMe2 Co-H···OH2 Mn-H···OMe2 Fe-H···OMe2 Co-H···OMe2

ρH 0.006 0.007 0.011 0.013 0.017 0.030 0.012 0.008 0.012 0.013 0.018 0.028 0.012 0.012 0.014 0.019

∇2ρH

0.016 0.017 0.023 0.026 0.031 0.043 0.024 0.018 0.024 0.025 0.030 0.036 0.032 0.030 0.033 0.049

ΔqH

ΔEH

Δ|MH|

ΔVH

ΔNH

ΔrH

0.024 0.062 0.086 0.080 0.107 0.207 0.042 0.056 0.088 0.080 0.111 0.204 0.115 0.092 0.116 0.172

0.004 0.020 0.039 0.025 0.038 0.103 0.013 0.019 0.041 0.025 0.044 0.103 0.048 0.024 0.036 0.073

-0.026 -0.019

-3.28 -5.83 -6.58 -14.92 -16.07 -18.17 -3.49 -5.85 -7.38 -14.66 -16.87 -17.57 -9.06 -14.08 -14.48 -14.79

-0.008 -0.049 -0.076 -0.062 -0.089 -0.195 -0.025 -0.042 -0.077 -0.060 -0.093 -0.192 -0.106 -0.074 -0.100 -0.160

1.398 1.265 1.741 1.837 2.247 2.360 1.510 1.603 1.966 2.014 2.487 2.452 1.696 1.794 2.081 2.139

0.001 -0.048 -0.051 -0.023 -0.017 -0.021 0.002 -0.045 -0.050 -0.005 -0.018 -0.055 -0.052 -0.026

We examined the proposed set of criteria by Koch and Popelier to illustrate the possible formation of M-H•••Y H-bonds on the basis of AIM theory.30 Following conclusions were obtained after M-H•••Y interactions were subjected to these criteria (See Table 2). 1.

Presence of BCP between H and Y (O, S, Se) atoms: We found BCPs in all the

complexes suggesting the formation of M-H•••Y H-bonds (Table 2).



2,3. The electron density, ρH and Laplacian of electron density ∇2ρH at BCP should be in the

range of 0.002–0.034 a.u. and 0.024–0.139 a.u., respectively. Depending on the basis set used small deviations can be expected in these ranges. All complexes fall within these ranges and satisfy the criteria.

4.

According to fourth criterion, the mutual penetration (ΔrH) between H atom and hydrogen

bond acceptor atom should be positive for H-bond formation. We observed positive ΔrH values for all the M-H•••Y H-bonded complexes. 5.

Charge reduction on hydrogen upon H-bond formation: This was obtained by subtracting

the electronic population of hydrogen atom in the free form (monomer) from the complex form (after complex formation). The difference in population i.e. ΔN should be negative. The ΔN values shown in Table 2 for all H-bond complexes are negative and satisfy this criterion. 6.

Hydrogen atom should be destabilized in the complex i.e. the energy difference of H

atom in the complex and monomer (ΔEH =EH (complex)- EH (monomer)) should be positive. The ΔEH values in Table 2 for all the complexes are positive, thus fulfilling this criterion. 7.

A reduction in dipolar polarization (Δ|MH|) should be observed for H atom upon complex

formation. Only two exceptions were noticed. 8.

This last criterion says that the atomic volume of H atom decreases on H-bond complex

formation i.e. ΔVH should be negative. All values of ΔVH in Table 2 are negative indicating Hbond formation. All the criteria proposed by Koch and Popelier are well satisfied, and thus confirming the formation of H-bonds in M-H•••Y complexes. The above mentioned criteria are regularly used to verify the formation of non-covalent interactions such as hydrogen bond30 and carbon bond etc.47


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Figure 3. Electron density topology analysis: (a) molecular graph for Fe(CO)4H2•••DMS H-Bond dimer; (b) colored isosurfaces of the reduced electron density gradient (3D-NCI-plot) for Fe-H•••S H-bond, the blue isosurface indicates attractive non-covalent interaction between Fe(CO)4H2 and DMS; (c) plot of the reduced density gradient (s) vs. the sign of the second Eigen value of the electron-density Hessian matrix (λ2) times electron density (sign(λ2)ρ(r)) for Fe(CO)4H2•••DMS H-Bond dimer, where the encircled represents bond critical point (BCP) of Fe-H•••S H-bond; (d) MESP surface of Fe(CO)4H2•••DMS HBond dimer mapped on 0.001 a.u. electron density surface; (e) H-bond length-electron density (ρc) correlation for M-H•••Y H-Bonds; (f) H-bond distance-hydrogen bond energy from AIM at BCP (EH•••Y vs. dH•••Y) correlation for M-H•••Y H-Bond dimers. The points 1 to 9 in above figure (e and f) are as follows

1:Mn(CO)5H•••DME,

5:Fe(CO)4H2•••DMS,

2:Mn(CO)5H•••DMS,

6:Fe(CO)4H2•••DMSe,

3:Mn(CO)5H•••DMSe,

7:Co(CO)4H•••DME,

4:Fe(CO)4H2•••DME,

8:Co(CO)4H•••DMS,

and

9:Co(CO)4H•••DMSe.

We performed non covalent interactions (NCI) analysis55 to illustrate the nature of all the M-H•••Y intermolecular H-bond complexes. Reduced density gradient (RDG) isosurfaces in real 3D space for Fe(CO)4H2•••DMS complex is shown in Figure 3b and the same for all other complexes are depicted in Figure S2-S4(d-f) in supporting information. Dark blue colored isosurfaces observed in M-H•••Y complexes are indication of strong attractive interactions56 while green colored isosurfaces show very weak van der Waals interactions between hydrogen atom of acceptors (DME, DMS and DMSe) and carbonyl groups of transition metal hydrides. ACS Paragon Plus Environment


Figure 3c shows a representative plot between reduced density gradient (RDG) and sign of second Eigen value of electron density Hessian matrix (λ2) times electron density for Fe(CO)4H2•••DMS complex to illustrate the nature of H-bond more quantitatively. The peaks in the plot lies in negative side having sign(λ2) ρc value of -0.012 au which is within the range of strong hydrogen bonds (−0.01 > sign(λ2)ρ > −0.06).57-58 Similar observations were also noticed for other complexes (see Figure S2-S4(g-i) in supporting information) indicating attractive and non-covalent nature of M-H•••Y interaction. We performed Molecular electrostatic potential (MESP)59 analysis of the M-H•••Y Hbond complexes. MESP for Fe(CO)4H2•••DME H-bond dimer as a representative example mapped on 0.001 a.u. electron density surface is plotted in Figure 3d. We can see electro negative potential (red coloured surface) of DME oxygen (electron rich with lone pair) overlaps with relatively positive potential surface (light blue) of Fe-H hydrogen leading to attractive σ hole interactions forming stable Fe(CO)4H2•••DME H-Bond dimer. MESP plots for all metal hydride complexes with DME, DMS and DMSe H-bond acceptors are presented in Figure S5. Spectroscopic observables and their correlation with M-H bond lengths and interaction energies Figure 4a shows computational M-H stretching frequencies of metal hydride Co(CO)4H in its free state and its bound state with different H-bond acceptors. Here, Co complex is taken as a representative example for frequency shift comparison. The red shift in the M-H stretching frequencies were observed for all the Co(CO)4H complexes with respect to that of the monomer. The red shift of M-H stretching frequencies for Co(CO)4H-DME Co(CO)4H-DMS and Co(CO)4H-DMSe complexes are 93 cm-1, 405 and 408 cm-1, respectively. These frequency shifts are in consistent with their binding energy values (see Table 1) for H-bonded complexes. This type of correlation has already been noticed for other H-bond complexes.60 Stronger the H-bond , more likely is the possibility of M-H frequency shift (red shift). As shown in Figures 4b,c; linear correlations were obtained between frequency shift (Δυ) vs. M-H bond length (dM-H), binding energy (ΔE)) with R2 > 0.9. The maximum M-H bond stretching (5 pm) corresponds to the maximum M-H stretching frequency (407 cm-1) of Co(CO)4H-DMSe complex. Exception to this behavior is Mn(CO)5H-DME complex in which a small contraction of Mn-H bond (0.4 pm) is observed with blue shift of 15 cm-1(see Table S2). The larger binding energy of Co(CO)4H-


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DMSe complex (30kJ/mol) is in agreement with above data as can be seen in Figure 4c. The MH bond stretch can be attributed to transfer of charge from proton acceptor to antibonding sigma M-H orbital (σ*M-H) which can be quantified on the basis of NBO second order perturbation energy (EDA) listed in Table S2. In these two correlations (Figure 4b,c), oxygen is found to form weaker hydrogen bonded complexes compared to its sulfur and selenium counterpart. The hydrogen bond strength and hence frequency shift can also be reflected in 1H NMR chemical shift of metal hydrides. From chemical intuition it is expected that stronger the hydrogen bond, more is the downfield shift of H atom involved in the H-bond. Figures 4d,e show correlation of downfield 1H NMR chemical shift (δ) with binding energy (BE) and frequency shift (Δυ) of metal hydride complexes. The chemical shifts observed in this work are within 1 to 8 ppm. Thus, strength of H-bond can be gauged from red shift in M-H vibrational frequencies as well as downfield 1H chemical shift. It can be noticed that these correlations also reflect the formation of stronger H-bonds with S and Se than its O counterpart.

Figure 4. (a) Vibrational frequencies in free Co(CO)4H and its complexes Co(CO)4H•••H2O, Co(CO)4H•••H2S, Co(CO)4H•••H2Se, Co(CO)4H•••DME, Co(CO)4H•••DMS, Co(CO)4H•••DMSe; (b) Correlation plot of frequency shift (Δυ) vs. M-H bond length (dM-H); Correlation plot of (c) BSSE corrected binding energy (ΔE) vs. frequency shift (Δυ); (d) ΔE vs. 1H chemical shift of metal hydride δH(ppm); (e) δH(ppm) vs. frequency shift (Δυ). The points 1 to 9 in above figure are as follows



1:Mn(CO)5H•••DME, 5:Fe(CO)4H2•••DMS,

2:Mn(CO)5H•••DMS, 6:Fe(CO)4H2•••DMSe,

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3:Mn(CO)5H•••DMSe, 7:Co(CO)4H•••DME,


8:Co(CO)4H•••DMS,

and

9:Co(CO)4H•••DMSe.

We further investigated these H-bonded complexes on the basis of the interaction between the donor-acceptor orbitals through natural bond orbital (NBO) analysis at MP2/aug-ccpVDZ. NBO formalism is a useful method to compute the interaction energy (EDA) between donor and acceptor orbitals by second order perturbative method.34 The two lone pair of electrons of O, S or Se atom (nY) interact with anti bonding M-H orbital (σ*M-H) (Figure 5a-b and Figure S6-S8). The overlap between nO and σ*M-H involves sp and p type oxygen lone pair orbitals whereas the overlap of nS/Se involves s and p type sulfur/selenium lone pair orbitals with σ*M-H. Thus nS/Se→σ*M-H involving more s character cause more charge transfer compared to their O counter part resulting more interaction energy for M-H•••S or M-H•••Se H-bonds than for MH•••O H-bonds (see Table S2). Figure 5c shows the relationship between donor-acceptor interaction energy (EDA) and dH•••Y. For a particular Y (O/S/Se), the EDA varies linearly with the dH•••Y. Irrespective of transition metals (Mn, Fe and Co), the EDA values are the highest for MH•••Se H-bond complexes followed by M-H•••S and M-H•••O H-bond complexes. Another aspect of interpreting H-bond is to correlate EDA with 1H NMR and IR spectral shifts (See Table S2). Linear correlation plots are obtained for EDA versus IR shift (Δυ) (Figure 5d) and 1H downfield chemical shift (Figure 5e).


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Figure 5. (a,b) Fe-H•••Y H-bond in Fe(CO)5H•••DMS complex as revealed by overlap of s and p-type sulfur lone pairs and σ*M-H orbital; Correlation plots of NBO donor-acceptor interaction energies with (c) H-bond distance- (EDA vs. dH•••Y); (d) M-H vibrational frequency shift (EDA vs. ΔυM-H) and (e) 1H chemical shift (EDA vs. δ). The points 1 to 9 in above figure (c,d,e) are as follows 1:Mn(CO)5H•••DME, 2:Mn(CO)5H•••DMS,

3:Mn(CO)5H•••DMSe,


5:Fe(CO)4H2•••DMS,

6:Fe(CO)4H2•••DMSe, 7:Co(CO)4H•••DME, 8:Co(CO)4H•••DMS, and 9:Co(CO)4H•••DMSe.

Energy decomposition analysis We performed localized molecular orbital energy decomposition analysis (LMOEDA) scheme as implemented in Gamess31-32 to unveil the nature M-H•••Y H-bonds. With this method, the total interaction energy can be decomposed into electrostatic (ES), exchange (EX), coulomb repulsion (RL), polarization (PL) and dispersion (DISP) components. Figures 6(a,b,c) show EDA plots of M-H•••O, M-H•••S, and M-H•••Se H-Bonds, respectively. Here columbic electrostatic



Figure 6. (a,b,c) Energy decomposition analysis of M-H•••Y H-Bond; ES: electrostatic, EX: exchange, RL: repulsion, PL: polarization, DISP: dispersion, ΔETotal: dimerization energy estimated at MP2/aug-ccpVDZ.

component was calculated by taking the sum of ES, EX and RL terms. It is observed that without the contributions of dispersion interaction none of the dimers are stable i.e. dispersion component is the largest. As expected the dispersion contribution is more for M-H•••S, and MH•••Se H-Bonds than M-H•••O H-Bonds. The dispersion energy for Co-H•••O/S/Se varies from 81 kJ/mol to 126 kJ/mol and larger than respective Mn and Fe complexes. The different energy contributions to total interaction energies are displayed in Figure 6(a,b,c). Dispersion is the largest energy contributor followed by electrostatics and polarization. Thus EDA analysis also explains why potential energy curves M-H•••Y H-Bond dimers are dissociative if one excludes long range dispersion contribution; vide supra (Figure 2).

CONCLUSIONS The significance of this work lies in the fact that electro negativities of Mn, Fe and Co are less than H atom in M-H bond (H-bond donor), but still they can form M-H•••Y H-bonds. The structural, electronic and energetics of M-H•••Y H-bond complexes are very similar to those of conventional O-H•••O, N-H•••O and N-H•••O=C H-bonds. As revealed from PE curves and LMOEDA, unlike conventional hydrogen bonds where electrostatics plays major role for the formation of H-bonded dimers, here dispersion contributes the maximum for the formation of MH•••Y H-bonds. Spectroscopic parameters such vibrational frequency shift and 1H NMR chemical shift which are routinely used to estimate the strength of H-Bonds qualitatively are well correlated with the H-bond energies, NBO donor-acceptor interaction energies, H•••Y H-bond


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distances, and AIM topology provide sufficient evidences for the formation of M-H•••Y H-bond. Thei energies of M-H•••Y H-bond complexes calculated by various computational methods such as NBO, AIM, LMOEDA, suggest that sulfur and selenium are better H-bond acceptors than oxygen in the formation of M-H•••Y H-bonds; thereby inferring that polarizabilities of Hacceptors should be taken in account while considering the M-H•••Y H-bonds. Thus electronegativity is not the sole factor to judge the strength of M-H•••Y H-bond rather polarizability and dispersion are the deciding factors here. The strength of M-H•••Y H-bond lies in the range of 5-30 kJ/mol which is comparable to that of conventional H-bonds such as OH•••O, N-H•••O and N-H•••O=C H-bonds etc. We hope that this work will guide the researchers to invoke the concept M-H•••Y H-bonds in proton/hydrogen/hydride transfer and catalysis with transition metal hydrides, in supramolecular chemistry and more importantly in designing new force fields.

ASSOCIATED CONTENT Supporting Information Topological parameters, PE curves, Molecular graphs, NCI plots, MESP surfaces, donoracceptor energy, frequency shifts, 1H NMR chemical shifts, change in M-H bond, NBO overlap plots, optimized geometries. AUTHOR INFORMATION Corresponding Author Dr. Himansu S. Biswal, E-mail: [email protected], Phone: +91-674-2494 186/185 ORCID: 0000-0003-0791-2259 Notes The authors declare no competing financial interest. ACKNOWLEDGEMENTS HSB acknowledges financial support from Department of Atomic Energy, Govt. of India.




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TOC Graphic:



Biography Himansu S. Biswal was born in Rampa, Jajpur, Odisha, India. He obtained his MSc. degree in Chemistry from Utkal University, Odisha, India in 2002. He received his Ph.D. from Tata Institute of Fundamental Research (TIFR), Mumbai, India, where he worked with Professor Sanjay Wategaonkar studying the sulfur centered hydrogen bonds with supersonic-jet spectroscopy. He was a postdoctoral fellow with Professor Michel Mons at CEA, Saclay, France, where he investigated structure and ultrafast excited state dynamics of peptides. Then he moved to Prof. Jennifer P. Ogilvie's research group at University of Michigan, USA to work on 2D-electronic spectroscopy. In 2012, he joined in the school of Chemical Sciences, National Institute of Science Education and Research (NISER), India and now working as an Associate Professor there he has established a research program focused on investigating unusual non-covalent interactions in biomolecules with electronic structure calculation, NMR, Raman and gas phase laser spectroscopy.


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82x36mm (300 x 300 DPI)



Metal carbonyl hydrides as H-bond donors: Mn(CO)5H, Fe(CO)4H2, Co(CO)4H; H-bond acceptors: H2S, DMS, H2Se, DMSe and DME; Optimized structures of H-bonded complexes of donors and acceptors at RIB97D/def2-TZVPPlevel. The bond distances are given in pm. 165x105mm (300 x 300 DPI)


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Potential energy (PE) curves of M-H•••Y H-Bond dimers: (a), (c) Mn(CO)5H•••DMS, Fe(CO)4H2•••DMS, Co(CO)4H•••DMS representing M-H•••S H-Bonds; (b), (d) Fe(CO)5H•••DME, Fe(CO)5H•••DMS, Fe(CO)5H•••DMSe representing Fe-H•••O, Fe-H•••S, Fe-H•••Se H-Bonds, respectively. Left part of the plot (a,b) represents PE curves without dispersion correction i.e. RI-B97D/def2-TZVPP without Grimme’s long range dispersion correction and right part of the plot (c,d) represents PE curves with dispersion i.e RI-B97D /def2-TZVPP with Grimme’s long range dispersion correction. BSSE is added to the dimerization energy. 165x162mm (300 x 300 DPI)



Electron density topology analysis: (a) molecular graph for Fe(CO)4H2•••DMS H-Bond dimer; (b) colored isosurfaces of the reduced electron density gradient (3D-NCI-plot) for Fe-H•••S H-bond, the blue isosurface indicates attractive non-covalent interaction between Fe(CO)4H2 and DMS; (c) plot of the reduced density gradient (s) vs. the sign of the second Eigen value of the electron-density Hessian matrix (λ2) times electron density (sign(λ2)ρ(r)) for Fe(CO)4H2•••DMS H-Bond dimer, where the encircled represents bond critical point (BCP) of Fe-H•••S H-bond; (d) MESP surface of Fe(CO)4H2•••DMS H-Bond dimer mapped on 0.001 a.u. electron density surface; (e) H-bond length-electron density (ρc) correlation for M-H•••Y HBonds; (f) H-bond distance-hydrogen bond energy from AIM at BCP (EH•••Y vs. dH•••Y) correlation for MH•••Y H-Bond dimers. The points 1 to 9 in above figure (e and f) are as follows 1:Mn(CO)5H•••DME, 2:Mn(CO)5H•••DMS, 3:Mn(CO)5H•••DMSe, 4:Fe(CO)4H2•••DME, 5:Fe(CO)4H2•••DMS, 6:Fe(CO)4H2•••DMSe, 7:Co(CO)4H•••DME, 8:Co(CO)4H•••DMS, and 9:Co(CO)4H•••DMSe. 165x91mm (300 x 300 DPI)


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(a) Vibrational frequencies in free Co(CO)4H and its complexes Co(CO)4H•••H2O, Co(CO)4H•••H2S, Co(CO)4H•••H2Se, Co(CO)4H•••DME, Co(CO)4H•••DMS, Co(CO)4H•••DMSe; (b) Correlation plot of frequency shift (Δυ) vs. M-H bond length (dM-H); Correlation plot of (c) BSSE corrected binding energy (ΔE) vs. frequency shift (Δυ); (d) ΔE vs. 1H chemical shift of metal hydride δH(ppm); (e) δH(ppm) vs. frequency shift (Δυ). The points 1 to 9 in above figure are as follows 1:Mn(CO)5H•••DME, 2:Mn(CO)5H•••DMS, 3:Mn(CO)5H•••DMSe, 4:Fe(CO)4H2•••DME, 5:Fe(CO)4H2•••DMS, 6:Fe(CO)4H2•••DMSe, 7:Co(CO)4H•••DME, 8:Co(CO)4H•••DMS, and 9:Co(CO)4H•••DMSe. 165x93mm (300 x 300 DPI)



(a,b) Fe-H•••Y H-bond in Fe(CO)5H•••DMS complex as revealed by overlap of s and p-type sulfur lone pairs and σ*M-H orbital; Correlation plots of NBO donor-acceptor interaction energies with (c) H-bond distance(EDA vs. dH•••Y); (d) M-H vibrational frequency shift (EDA vs. ΔυM-H) and (e) 1H chemical shift (EDA vs. δ). The points 1 to 9 in above figure (c,d,e) are as follows 1:Mn(CO)5H•••DME, 2:Mn(CO)5H•••DMS, 3:Mn(CO)5H•••DMSe, 4:Fe(CO)4H2•••DME, 5:Fe(CO)4H2•••DMS, 6:Fe(CO)4H2•••DMSe, 7:Co(CO)4H•••DME, 8:Co(CO)4H•••DMS, and 9:Co(CO)4H•••DMSe. 165x97mm (300 x 300 DPI)


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(a,b,c) Energy decomposition analysis of M-H•••Y H-Bond; ES: electrostatic, EX: exchange, RL: repulsion, PL: polarization, DISP: dispersion, ΔETotal: dimerization energy estimated at MP2/aug-cc-pVDZ. 165x57mm (300 x 300 DPI)


(M = Mn, Fe, & Co) Hydrogen Bond - ACS Publications - American

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