Structure of [Pt(C6H5)2(btz-N,N')].CHCl3, btz = 2,2'-bi-5,6-dihydro-4H-1,3-thiazine

Brunò, Giuseppe; Lanza, Santo; Nicolò, Francesco

doi:10.1107/s010827018900778x

Cited by 18 publications

(12 citation statements)

References 3 publications

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“…In the following we have inspected the potential energy surface of η 1 (C–H)Pt moieties experimentally by high‐pressure X‐ray diffraction and infrared spectroscopy studies to gain further insight into the control parameters of the C–H activation process and the unusual bonding in square‐pyramidal d 8 ‐Pt chloroform complexes. The experimental model system d 8 ‐Pt(btz‐ N , N ′)(phenyl) 2 · (CHCl 3 ) ( 2 ) which has first been isolated by Bruno et al marked the starting point of this systematic study (Figure a). 2 displays a short r (Pt ··· H br ) distance of 2.315 [2.332] Å and a Pt ··· H br bond critical point of 0.20 e Å –3 in the theoretical electron density distribution obtained by DFT which is slightly smaller than in model system 1b (see above).…”

Section: Methodsmentioning

confidence: 99%

Pressure‐Enhanced C–H Bond Activation in Chloromethane Platinum(II) Complexes

et al. 2019

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The nature of the interaction between chloromethanes CH 4-n Cl n and Pt(II) complexes has been studied by highpressure X-ray diffraction and infrared spectroscopy in combination with DFT calculations. In case of electron rich complexes such as d 8 -Pt(btz-N,N′)(phenyl)L with L = phenyl, Cl, Br and btz = 2,2′-Bi-5,6-dihydro-4H-1,3-thiazine stable chloroform adducts with bridging hydrogen atoms in the η 1 (C-H)Pt moieties were isolated which display highly activated C-H bonds. This activa-The activation of carbon-hydrogen bonds is usually hampered by their rather apolar covalent character and large bond dissociation energies. For example the C-H bond dissociation enthalpies in simple alkanes such as methane [DH 298 = 439.28(13) kJ mol -1 ] are virtually as large as in the H 2 molecule [DH 298 = 435.998(13) kJ mol -1 ] displaying the prototype of a strong covalent bond. [1] As a consequence, alkanes are neither good electron donors nor good acceptors since the σ(C-H) bonding orbital is low in energy while the antibonding σ*(C-H) orbital is high lying. Hence, C-H bonds are generally considered to be chemically rather inert and their selective activation remains a challenge in organometallic chemistry. [2][3][4] This obstacle can be overcome by metal-assisted C-H bond activation in cases where an alkane ligand coordinates either end-on (η 1 ) or side-on (η 2 ) to a metal-ligand fragment ML n (Scheme 1). [5,6] In case of electron-rich late transition metal complexes two bonding scenarios with short M···H br -C contacts are usually observed for methane and halomethane d 8 -Pt complexes, where H br denotes a bridging hydrogen atom. These are illustrated in case of the theoretical model systems (CH 3 ) 2 Pt(NH 3 )(CH 4 ) 1a and (CH 3 ) 2 Pt(NH 3 ) 2 ·(CHCl 3 ) 1b in Scheme 1. We note, that all DFT calculations were performed with ADF using the BP86 functional, the ZORA for the descrip- [a]

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Section: Methodsmentioning

confidence: 99%

Pressure‐Enhanced C–H Bond Activation in Chloromethane Platinum(II) Complexes

et al. 2019

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“…An example of PtииииH-C intermolecular interaction is known. The crystal structure of the complex cis-[Pt(C 6 H 5 ) 2 {2,2′bis(5,6-dihydro-4H-1,3-thiazine-N,N′)}] (11) (29) has shown that the hydrogen atom of a molecule of chloroform, used as crystallization solvent, is located 2.48 Å from the platinum atom, the Pt-H-C angle being 169°. Note that the polarity of the C-H bond is enhanced by the presence of the electronegative substituents bonded to the carbon atom.…”

Section: Mииииh-x Intermolecular Hydrogen Bondsmentioning

confidence: 99%

Hydrogen Bonds Involving Transition Metal Centers Acting As Proton Acceptors

Martín¹

1999

J. Chem. Educ.

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A short review of the most remarkable results which have recently reported M----H-X hydrogen bonds, along with a systematization of their structural and spectroscopic properties, is provided in this paper. These M----H interactions are substantially different from the "agostic" M----H ones, and their differences are commented on, setting up criteria that permit their clear differentiation in order to avoid some of the misidentifications that occurred in the past.

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“…Two structurally characterized neutral complexes showing an intermolecular XÀH···Pt interaction (X = N or C) have indicated, however, that even intermolecular H bonding not aided by ionic forces is energetically feasible. [10,11] A ubiquitous and excellent hydrogen-bond donor is water, and the question arises whether in aqueous solutions of square-planar d 8 metal complexes, axial water molecules could form hydrogen bonds to the metal atom. We have previously reported Møller-Plesset second-order perturbation theory (MP2) calculations predicting that neutral Pt II complexes, when interacting with an H 2 O molecule in an axial position, prefer its "H-ahead" orientation, corresponding to an O À H···Pt hydrogen bond.…”

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Dispersion‐Driven Hydrogen Bonding: Predicted Hydrogen Bond between Water and Platinum(II) Identified by Neutron Diffraction

et al. 2010

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An alternative to classical? In square‐planar d8 complexes the metal ion can interact with axial H2O molecules either as a Lewis acid or as a Lewis base. Ab initio calculations predicted that uncharged PtII complexes form a hydrogen‐bond‐like interaction with H2O, in which PtII acts as a Lewis base. Such a nonclassical OH⋅⋅⋅Pt hydrogen bond has now been identified in crystals of trans‐[PtCl2(NH3)(N‐glycine)]⋅H2O by neutron diffraction.

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Structure of [Pt(C6H5)2(btz-N,N')].CHCl3, btz = 2,2'-bi-5,6-dihydro-4H-1,3-thiazine

Abstract: Abstract. ( 2

Cited by 18 publications

References 3 publications

Pressure‐Enhanced C–H Bond Activation in Chloromethane Platinum(II) Complexes

Pressure‐Enhanced C–H Bond Activation in Chloromethane Platinum(II) Complexes

Hydrogen Bonds Involving Transition Metal Centers Acting As Proton Acceptors

Dispersion‐Driven Hydrogen Bonding: Predicted Hydrogen Bond between Water and Platinum(II) Identified by Neutron Diffraction

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