Heterotridentate Organomonophosphines in Pt(η3-P1C1C2)(Y) and Pt(η3-P1C1N1)(Y) Derivatives—Structural Aspects

Melník, Milan; Mikušová, Veronika; Mikuš, Peter

doi:10.3390/inorganics11080338

Open AccessCommunication

Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects

by

Milan Melník

^1,*,

Veronika Mikušová

² and

Peter Mikuš

^1,3,*

¹

Department of Pharmaceutical Analysis and Nuclear Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovakia

²

Department of Galenic Pharmacy, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovakia

³

Toxicological and Antidoping Centre, Faculty of Pharmacy, Comenius University Bratislava, Odbojárov 10, SK-832 32 Bratislava, Slovakia

^*

Authors to whom correspondence should be addressed.

Inorganics 2023, 11(8), 338; https://doi.org/10.3390/inorganics11080338

Submission received: 24 July 2023 / Revised: 11 August 2023 / Accepted: 14 August 2023 / Published: 16 August 2023

(This article belongs to the Section Inorganic Materials)

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Abstract

:

This paper covers Pt(II) complexes of the compositions Pt(η³-P¹C¹C²)(Y) (Y = NL or I) and Pt(η³-P¹C¹N¹)(Y), Y = OL, NL, CL, Cl or Br). These complexes crystallized in four crystal classes: monoclinic (9 examples), triclinic (3 examples), orthorhombic (3 examples), and tetragonal (2 examples). The structural parameters (Pt-L, L-Pt-L) are analyzed and discussed with attention to the distortion of square-planar geometry about the Pt(II) atoms and trans-influence. These data are compared and discussed with those of Pt(η³-P¹N¹N²)(Y), Pt(η³-P¹N¹X¹)(Y), (X¹=O¹, C¹, S¹, Se¹), Pt(η³-N¹P¹N²)(Cl), Pt(η³-S¹P¹S²)(Cl), Pt(η³-P¹S¹Cl¹)(Cl), and Pt(η³-P¹Si¹N¹)(OL) types. Each heterotridentate ligand creates two metallocyclic rings with a common central ligating atom. These η³-ligands form twenty-three types of metallocycles and differ by the number and type of the atoms involved in the metallocyclic rings.

Keywords:

structure; heterotridentate; organomonophosphines; Pt(II); distortion

Graphical Abstract

1. Introduction

Platinum compounds have significantly established themselves in the areas of biochemistry [1], catalysis [2,3,4,5], spectroscopy [6,7], and coordination theory. Very recently, a valuable review focused on the importance and advances in synthetic, structural, thermodynamic, electronic, and photophysical properties of Pt-based heteropolynuclear complexes was published [8].

Organophosphines, a soft P-donor ligand are very useful for building a wide variety of platinum complexes. We classified and analyzed structural data of monomeric platinum(II) coordination complexes with an inner coordination sphere: PtP₄, PtP₃X (X = H, F, O, N, Cl, S, Br, or I), and PtP_{2 × 2} (X = H, F, O, N, CN or B) in which P-donor ligands are monodentate organomonophosphines [9]. Recently, we classified and analyzed structural data of monomeric heterotridentate organomonophosphines with inner coordination spheres, Pt(η³-P¹N¹N²)(Y) (Y = CH₃ or Cl), Pt(η³-P¹N¹X¹)(Y) (X¹ = O¹, Y = P²L, Cl or I), (X¹ = C¹, Y = N³L, Cl or Br); (X¹ = S¹; Y = Cl), and (X¹ = Se¹, Y = Cl) [10]. A very recent paper analyzed and classified X-ray data of homotridentate ligands of the Pt(η³-X¹X²X³)(PR₃), (X = N¹, N², N³; S¹, S², S³; or Te¹, Te², Te³) [11]. These structural studies were based on the analysis of crystallographic data. Among many other analysis methods (IR, TGA, etc.), another powerful approach for structural studies of complexes and confirming their conformations is DTF (density functional theory) as a quantum-mechanical atomistic simulation method, demonstrating recently, e.g., in refs. [12,13].

This survey aims to classify and analyze structural parameters of another class of organophoshine structures, namely Pt(η³-P¹C¹C²)(Y) (Y = NL, or I) and Pt(η³-P¹C¹N¹)(Y), (Y = OL, NL, Cl or Br). The data are discussed and compared with Pt(η³-P¹N¹N²)(Y) and Pt (η³-P¹N¹X¹)(Y) structures. This structural study was based on the analysis of crystallographic data that were available, unlike other methods of structural analysis, for all complexes involved in this work.

2. Results and Discussion

2.1. Pt(η³-P¹C¹C²)(Y) Type

There are five examples of Pt(η³-P¹C¹C²)(Y) type, and their structural data are gathered in Table 1. In four of them: orthorhombic [Pt{η³-Bu^t₂P(C₁₈H₁₃)}(py)] (at 110 K), and three monoclinic [Pt{η³-Bu^t₂P(C₁₈H₁₃O)}(NCCH₃)] (at 110 K), [Pt{η³-Bu^t₂P(C₁₇H₉F₂)}(NCCH₃)] (at 110 K), and [Pt{η³-Bu^t₂P(C₁₇ H₁₀F)}(NCCH₃)] (at 110 K) [14] a distorted square-planar geometry about Pt is build up by η³-P¹C¹C² ligand and monodentate N donor atom/ligand. The structure of [Pt{η³-Bu^t₂P(C₁₈H₁₃)}(py)] [14] is shown in Figure 1 as an example. Each η³-ligand forms two five-membered metallocyclic rings with a common C¹ atom of the P¹C₂C¹C₂C² type. The mean values of the respective chelate L-Pt-L bond angles are 83.4 (±8)° (P¹-Pt-C¹) and 81.1 (±4)° (C¹-Pt-C²). The remaining L-Pt-L bond angles open in the order (mean values): 94.5 (±2.5)° (C²-Pt-N) < 103.0 (±8)° (P¹-Pt-N) <163. 9 (±7)° (P¹-P¹-C²) < 171.8 (±7)° (C¹-Pt-N). The Pt-L bond distance elongates in the order (mean values): 1.977 (±4) Å (Pt-C¹, trans N) < 2.054 (±10) Å (Pt-C², trans to P¹) < 2.067 (±12) Å (Pt-N) < 2.327 (±11) Å (Pt-P¹).

In triclinic [Pt{η³-Ph₂P(CH₂C(Me)=CPPh₂(C₆H₄Ph)}(I)] (at 100K) [15], heterotridentate ligand creates two five-membered metallocyclic rings of the P¹C₂C¹PCC² type, with the values of the respective chelate L-Pt-L bond angles of 79.3° (P¹-Pt-C¹) and 86.0° (C¹-Pt-C²). The remaining L-Pt-L bond angles open in the order: 96.3° (C²-Pt-I) < 98.5° (P¹-Pt-I) < 165.0° (P¹-Pt-C²) < 175.9° (C¹-Pt-I). The Pt-L bond distance elongates in the order: 2.010 Å (Pt-C¹) < 2.042 Å (Pt-C²) < 2. 269 Å (Pt-P¹) < 2. 663 Å (Pt-I).

2.2. Pt(η³-P¹C¹N¹)(Y) Type

There are thirteen examples of Pt(η³-P¹C¹N¹)(Y) type, and their structural data are given in Table 2.

2.2.1. Pt(η³-P¹C¹N¹)(OL) Type

In three complexes, two monoclinic [Pt{η³-Bu^t₂P(C₉H₉NMe₂)}(OH)] (at 120 K), [Pt{η³-Bu^t₂P(C₉H₉NMe₂)}(H₂O)]BF₄.thf (at 120 K) and orthorhombic [Pt{η³-Bu^t₂P(C₉H₉NMe₂)} (OS(=O)₂CF₃)] (at 120 K) [16] a distorted square planar geometry about Pt(II) atom is built up by η³-P¹C¹N¹ ligand and monodentate OL. Each heterotridentate ligand creates two metallocyclic rings, each one five- and six-membered with common C¹ atom of the type P¹C₂C¹C₃N¹ with the mean values of the respective chelate L-Pt-L bond angles of 84.1 (±4)° (P¹-Pt-C¹) and 95.5 (±4)° (C¹-Pt-N¹). The remaining L-Pt-L bond angles open in the order (mean values): 86.0 (±1.2)° (N¹-Pt-O) < 94.6 (±1.6)° (P¹-Pt-O) < 174.6 (±7)° (P1-Pt-N¹) < 175.9 (±2.7)° (C¹-Pt-O). The Pt-L bond distance elongates in the order (mean values): 2.007 (± 13] Å (Pt-C¹, trans to O) < 2.166 (±2) Å (Pt-N¹, trans to P¹) < 2.175 (±5) Å (Pt-O) < 2.229 (±19) (Pt-P¹).

2.2.2. Pt (η^3-P¹C¹N¹)(CL) Type

In another three complexes, monoclinic [Pt{η³-Bu^t₂P(C₉H₉NMe₂)}(CO)]BF₄ (at 120 K) [15], tetragonal [Pt{η³-Bu^t₂P(C₉H₉NMe₂)}(CH₃)] (at 120 K) [17], and triclinic [Pt{η³-Bu^t₂P(C₉H₉NMe₂)}{C(Ph)=N=N}] (at 120 K) [17] the η³-P¹C¹N¹ ligand with monodentate C-donor ligand completed a distorted square planar geometry (PtP¹C¹N¹C). The heterotridentate ligand created five- and six-membered metallocyclic rings with a common C¹ atom of the P¹C₂C¹C₃N¹ type. The mean values of the respective chelate L-Pt-L bond angles are 83.4 (±4)° (P¹-Pt-C¹) and 91.8 (±2.5)° (C¹-Pt-N¹). The remaining L-Pt-L bond angles open in the order (mean values): 90.7 (±3.7)° (N¹-Pt-C) < 94.9 (±1.9) (P¹-Pt-C) < 171.8 (±3.8)° (P¹-Pt-N¹) < 172.3 (±2.8)° (C¹-Pt-C). The Pt-L bond distance elongates in the order (mean values): 2.064 (±9) Å Pt-C¹, trans to C) < 2.080 (±16) Å (Pt-C) < 2.175 (±12) Å (Pt-N¹, trans to P¹) < 2.232 (±25) Å (Pt-P¹).

2.2.3. Pt(η³-P¹C¹N¹)(Cl) Type

There are four complexes of this type. In monoclinic [Pt{η³-Bu^t₂P(C₈H₇NEt₂)}(Cl)] (at 120 K) [16] the η³-ligand creates two five-membered metallocyclic rings with common C¹ atom of the P¹C₂C¹C₂N¹ type. The values of the respective chelate L-Pt-L bond angles are 83.6° (P¹-Pt-C¹) and 82.8° (C¹-Pt-N¹). The remaining angles are 97.2° (N¹-Pt-Cl), 100.5° (P¹-Pt-Cl), 166.2° (P¹-Pt-N¹), and 174.3° (C¹-Pt-Cl).

In another monoclinic [Pt{η³-Bu^t₂P(C₉H₉NMe₂)}(Cl)] (at 120 K) [17], heterotridentate ligand creates five- and six-membered metallocyclic rings with common C¹ atom of the P¹C₂C¹C₃ N¹ type. The values of the respective L-Pt-L bond angles are 84.8° (P¹-Pt-C¹) and 94.4° (C¹-Pt-N¹). The values for remaining L-PL-L bond angles open in the order: 87.2° (N¹-Pt-Cl) < 93.9° (P¹-Pt-Cl) < 174.2° (P¹-Pt-N¹) < 174.8° (C¹-Pt-Cl).

In triclinic [Pt{η³-Ph₂P(C₁₆H₁₃NMe₂)}(Cl)] (at 103 K) [19] the η³-ligand forms P¹C₃C¹C₂N¹ type with the values of L-Pt-L chelate angles of 95.9° (P¹-Pt-C¹) and 82.2° (C¹-Pt-N¹). The remaining L-Pt-L bond angles open in the order: 89.5° (P¹-Pt-Cl) < 92.6° (N¹-Pt-Cl) < 174.4° (C¹-Pt-Cl) < 176.1° (P¹-Pt-N¹).

The P¹C₃NC¹NC₃N¹ type was formed in tetragonal [Pt{η³-Ph₂P(C₂₃H₂₈N₃)}(Cl)]PF₆.thf Figure 2 [20]. The values of chelate L-Pt-L angles are 92.8° (P¹-Pt-C¹) and 86.1° (C¹-Pt-N¹). The remaining L-Pt-L bond angles open in the order 87.1° (N¹-Pt-Cl) < 93.8° (P¹-Pt-Cl) < 171.3° (C¹-Pt-Cl) < 178.2° (P¹-Pt-N¹).

The Cl⁻ completed a distorted square planar geometry in these complexes about each Pt(II) atom. The Pt-L bond distance elongates in the order (mean values): 1.994 (±26) Å (Pt-C¹, trans to Cl) < 2.151 (±25) Å (Pt-N¹), trans to P¹) < 2.223 (±15) Å (Pt-P¹) < 2.389 (±72) Å (Pt-Cl).

2.2.4. Pt(η³-P¹C¹N¹)(Y) (Y = NL, Br) Type

Monoclinic [Pt{η³-Ph₂P(C₈H₆O₂NPh)}(NCCH₃)]BF₄ (at 110 K) [21] is the only example in which a η³-ligand with monodentate NCCH₃ ligand built up a distorted square planar geometry about Pt(II) atom. The heterotridentate ligand creates two five-membered metallocyclic rings of the P¹OCC¹C₂N¹ type. The values of the respective chelate L-PL-L bond angles are 80.3° (P¹-Pt-C¹), and 79.4° (C¹-Pt-N¹). The remaining L-Pt-L bond angles open in the order: 96.3° (N¹-Pt-N) < 104.1° (P¹-Pt-N) < 159.2° (P¹-Pt-N¹) < 174.4° (C¹-Pt-N). The Pt-L bond distance elongates in the order: 1.950 Å (Pt-C¹, trans to N) < 2.066 Å (Pt-N) < 2.127 Å (Pt-N¹) < 2.200 Å (Pt-P¹, trans to N¹).

In two orthorhombic [Pt{η³-Ph₂P(C₈H₆O₂NPh)}(Br)] (at 150 K) [21] and [Pt{η³-Prⁱ₂P(C₁₁H₁₅NO₂)}(Br)] (at 150 K) [22], each η³-ligand creates two five-membered metallocyclic rings with common C¹ atom of the P¹OCC¹C₂N¹ type. The values of the respective chelate L-Pt-L bond angles (mean values) are 81.6° (P¹-Pt-C¹) and 79.5° (C¹-Pt-N¹). The remaining L-Pt-L bond angle open in the order (mean values): 98.3° (N¹-Pt-Br) < 100.3° (P¹-Pt-Br) < 159.6° (P¹-Pt-N¹) < 176.9° (C¹-Pt-Br). The Pt-L bond distance elongates in the order (mean values): 1.956 Å (Pt-C¹) < 2.163 Å (Pt-N¹) < 2.179 Å (Pt-P¹) < 2. 498 Å (Pt-Br).

3. Conclusions

This paper includes eighteen monomeric Pt(II) complexes with compositions Pt(η³-P¹C¹C²)(Y) (Y = NL, or I) and Pt(η³-P¹C¹N¹)(Y), (Y = OL, NL, CL, Cl or Br). Recently, we classified and analyzed structural parameters of Pt(η³-P¹N¹N²)(Y), (Y = CL or Cl); Pt(η³-P¹N¹O¹)(Y), (Y = PL, Cl or I); Pt(η³-P¹N¹C¹)(Y), (Y = NL or Cl); Pt(η³-P¹N¹S¹)(Y), (Y = Cl or I); Pt(η³-P¹N¹Si¹)(Cl); Pt(η³-N¹P¹N²)(Cl); Pt(η³–S¹P¹S²)(Cl); Pt(η³-P¹S¹Cl¹)(Cl) and Pt(η³-P¹Si¹N¹)(OL) [10].

Each heterotridentate ligand creates two metallocyclic rings. These eleven sub-groups of η³-ligands build up twenty-three metallocycles types. These types based on the membered number of atoms in the chelate L-Pt-L angles with mean values are:

5+5: P¹C₂C¹C₂C², P¹C₂C¹PCC², P¹C₂C¹C₂N¹, P²OCC¹C₂N¹, P¹C₂N¹C₂N², P¹C₂N¹NCO¹, P¹C₂N¹NCC¹, S¹C₂P¹C₂S²; Σ 84.6/82.6°

5+6: P¹C₂C¹C₃N¹, P¹C₂N¹C₃O¹, P¹C₂S¹C₂BCl¹, P¹C₂Si¹C₃N¹; Σ 85.5/92.9°

6+5: P¹C₃C¹C₂N¹, P¹C₃N¹C₂N², P¹C₃N¹NCN², P¹C₃N¹C₂C¹, P¹C₃N¹NCS¹; Σ 94.4/83.8°

6+6: P¹C₃N¹C₃N², P¹C₃N¹C₃O¹, P¹C₃N¹C₃S¹, P¹C₃N¹C₃Se¹; Σ 91.1/91.7°

7+7: P¹C₃NC¹NC₃N¹; Σ 92.8/86.1°

There are at least two contributing factors to the size of the chelate bond angles both ligands based. One is the steric constraints imposed on the ligand and the other is the need to accommodate tridenticity where appropriate.

The Pt-P¹ (trans to X¹) bond distance elongates in the sequence (total mean values): 2.198 Å (X = Cl) < 2.206 Å (N²) < 2. 211 Å (O¹) < 2. 215 Å (N¹) < 2.239 Å (S¹) < 2.260 Å (C¹) < 2.327 Å (CL) < 2.407 Å (Se¹).

The Pt-Y (trans to X¹) bond distances elongate in the sequences: (total mean values):

Pt-NL: 2.02 Å (N¹) < 2.097 Å (C¹); Pt-OL: 2.175 Å (C¹) < 2.353 Å (Si¹);

Pt-CL: 2.068 Å (N¹) < 2.085 Å (C¹); Pt-Cl: 2.332 Å (N¹) < 2.372 Å (P¹) < 2.380 Å (S¹) < 2.389 Å (C¹); Pt-PL: 2.265 Å (N¹); Pt-Br: 2.490 Å (C¹); Pt-I: 2.590 Å (N¹) < 2.663 Å (C¹). These values correspond quite well with the trans influence of the respective X¹-donor atoms.

In transition metal complexes, the oxidation state plays a leading role in the geometry formed and platinum is no exception. In four coordinate Pt(II) prefers a square planar geometry. The utility of a simple metric to assess molecule shape and degree of distortion best exemplified the τ₄ parameter via an equation introduced by [23]:

τ_{4} = \frac{360 - (α + β)}{141}

where β and α are the two largest angles and assume the value of 0 and 1 for the perfect square planar and perfect tetrahedral geometries, respectively.

The total mean values of τ₄ and some structural parameters for the respective metallocycles are gathered in the following summary in Table 3:

It is well known that a distortion of a square-planar geometry around a metal atom diminishes with opening trans-L-Pt-L angles. As can be seen, the membered of metallocycles also play a role. When the sums of a “pair” of the respective L-Pt-L chelate, the angles distortion decreases.

We believe that such a structural analysis can continue to serve a useful function by centralizing available material in a wide scale of Pt complexes and delineating areas worthy of further investigation.

Author Contributions

Conceptualization, M.M. and P.M.; methodology M.M. and P.M.; Writing—Original draft preparation, M.M. and P.M.; data curation, M.M.; Writing—Review and editing, V.M.; supervision, M.M. and P.M.; funding acquisition, P.M. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the project VEGA 1/0514/22, VEGA 1/0146/23.

Data Availability Statement

Data supporting reported results can be found at author M.M.

Acknowledgments

This work was supported by the Faculty of Pharmacy, Comenius University Bratislava.

Conflicts of Interest

The authors declare no conflict of interest.

Abbreviations

Bu^t₂P(C₈H₇NEt₂)	(2-((di-t-butylphosphino)methyl)-6-((diethylamino)methyl) phenyl)
Bu^t₂P(C₁₈H₁₃O)	(8-(di-t-butylphosphanyl)-7-methy-2-(4-methoxybenzene-1,2-diyl) naphthalene-1-yl)
Bu^t₂P(C₁₇H₁₀F)	(8-(di-t-butylphosphanyl)-7-methyl-2-(4-fluorobenzene-1,2-diyl) naphthalene-1-yl)
Bu^t₂P(C₁₇H₉F₂)	(8-(di-t-butylphosphanyl)-7-methyl-2-(3,5-difluorobenzene-1,2-diyl) naphthalene-1-yl)
Bu^t₂P(C₁₈H₁₃)	(8-(di-t-butylphosphanyl)-7-methyl-2-(6-methylbenzen-1,2-yl) naphthalen-1-yl)
Bu^t₂P(C₉H₉NMe₂)	(2-dimethylamino)ethyl)-6-2-(di-t-butylphosphinomethyl)-6-phenyl)
m	monoclinic
or	orthorhombic
Ph₂P(C₁₆H₁₃NMe₂)	(2-(1-(dimethylamino)ethyl)-6-(2-diphenylphosphino)-2-phenylvinyl)phenyl)
Ph₂P(C₂₃H₂₈N₃)	(2-(2-(diphenylphoshino)benzyl)-1,8,8-trimethyl-4-(1-(pyridine-2-yl)ethyl)-2,4-diazobicyclo [9.2.1]octan-3-ylidene)
Ph₂P(C₈H₆O₂NPh)	(2-((diphenylphosphino)oxy)-3-methoxy-6-(phenylimino) methyl)phenyl)
Ph₂P(CH₂C(Me)=C	(3-(2-(2-methyl-3-diphenylphosphinopropenyl)
Ph₂P(C₆H₄Ph)	diphenylphosphino)biphenyl
Prⁱ₂P(C₇H₅ONC₄H₈0)	(2-((di-isopropylphosphino)oxy)-6-morpholino-4-yl)methyl)phenyl)
py	pyridine
tg	tetragonal
tr	triclinic
Te^1,2,3	represents ligating Te atoms differing in distances/angles with Pt atoms
P¹C₂C¹C₂C² (and sim.)	superscripts represent the ligating donor atoms, in case of the same atoms they are differing in distances/angles with Pt atoms; subscripts represent atoms which are located between the respective donor atoms
NL, OL, CL	N-donor ligand, O-donor ligand, C-donor ligand, respectively

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Figure 1. Structure of [Pt{η³-Bu^t₂P(C₁₈H₁₃)}(py) [14].

Figure 2. Structure of [Pt{η³-Ph₂P(C₂₃H₂₈N₃)}(Cl)] [20].

Table 1. Structural data for Pt(η³-P¹C¹C²)(Y) derivatives.

Complex Pt(η³-P¹C¹C²)(Y)	Crystal cl. Space gr. Z	a [Å] b [Å] c [Å]	α [°] β [°] γ [°]	Chromophore Chelate Rings τ₄ ^b	Pt-L ^a [Å]	L-Pt-L ^a [Å]	Ref.
[Pt{(η³-Bu^t₂P(C₁₈H₁₃)}(py)] (at 110 K)	or P2₁2₁2₁ 4	11.100(0) 12.121(0) 19.413(1)		Pt P¹C¹C²N (P¹C₂C¹C₂C²) 0.171	P¹ 2.328(1) C^1.1.973(3) C² 2.045(3) pyN 2.054(2)	P¹,C¹ 84.2 ^c C¹,C² 81.2 ^c P¹,C² 165.2 P¹,N 103.4 C²,N 99.4 C¹,N 170.7	[14]
[Pt{η³-Bu^t₂P(C₁₈H₁₃O)}. (NCCH₃)] (at 110 K)	m P2₁/n 4	18.058(0) 7.318(0) 19.792(0)	112.25(0)	PtP¹C¹C²N (P¹C₂C¹C₂C²) 0.181	P¹ 2.335(1) C^1.1.981(2) C² 2.052(2) LN 2.081(2)	P¹,C¹ 83.2 ^c C¹,C² 81.4 ^c P¹,C² 163.0 P¹,N 103.9 C²,N 92.0 C¹,N 171.3	[14]
[Pt{η³-Bu^t₂P(C₁₇H₉F₂)}. P(N=CCH₃)] (at 110 K)	m P2₁/n 4	16.434(0) 8.353(0) 17.385(0)	97.56(0)	PtP¹C¹C²N (P¹C₂C¹C₂C²) 0.163	P¹ 2.316(2) C¹ 1.973(3) C² 2.067(2) LN 2.078(2)	P¹,C¹ 83.2 ^c C¹,C² 80.7 ^c P¹,C² 164.0 P¹,N 101.3 C²,N 94.6 C¹,N 172.8	[14]
[Pt{η³-Bu^t₂P(C₁₇H₁₀F)}. (NCCH₃)] (at 110 K)	m P2₁/c 4	17.177(0) 7.446(0) 21.247(0)	106.10(0)	PtP¹C¹C²N (P¹C₂C¹C₂C²) 0.171	P¹ 2.329(2) C¹ 1.975(3) C² 2.068(3) LN 2.057(2)	P¹,C¹ 83.2 ^c C¹,C² 81.3 ^c P¹,C² 163.5 P¹,N 103.2 C²,N 92.1 C¹,N 172.3	[14]
[Pt{η³-Ph₂P¹(CH₂C(Me)=C PPh₂(C₆H₄Ph)}(I)] (at 100 K)	tr P $\bar{1}$ 2	9.822(1) 13.373(2) 14.254(2)	65.30(3) 78.17(3) 72.61(3)	PtP¹C¹C²I (P¹C₂C¹PCC²) 0.135	P¹ 2.269(1) C¹ 2.010(4) C² 2.042(4) I 2.663(1)	P¹,C¹ 79.3(1) C¹,C² 86.0(1) P¹,C² 165.0(1) P¹,I 98.5(1) C²,I 96.3(1) C¹,I 175.9(1)	[15]

Footer: ^a. The chemical identity of the coordinated atom/ligand is specified in these columns; ^b. The parameter τ4 specifies a degree of distortion; ^c. Five-membered metallocyclic ring.

Table 2. Structural data for Pt(η³-P¹C¹N¹)(Y) derivatives.

Complex Pt(η³-P¹C¹N¹)(Y)	Crystal cl. Space gr. Z	a [Å] b [Å] c [Å]	α [°] β [°] γ [°]	Chromophore Chelate Rings τ₄ ^b	Pt-L ^a [Å]	L-Pt-L ^a [Å]	Ref.
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)}. (OH)] (at 120 k)	m P2₁/c 4	20.075(4) 7.978(1) 12.800(3)	104.26(3)	PtP¹C¹N¹O (P¹C₂C¹C₃N¹) 0.046	P¹ 2.207(1) C¹ 2.021(2) N¹ 2.165(2) HO 2.094(2)	P¹,C¹ 83.7 ^c C²_,N ¹ 95.5 ^c P¹,N¹ 175.6 P¹,O 97.3 N¹,O 83.6 C¹,O 177.8	[16]
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)]. (H₂O)]BF₄.thf (at 120 K)	m P2₁/c 4	9.56(0) 14.941(0) 18.948(0)	97.12(0)	PtP¹C¹N¹O (P¹C₂C¹C₃N¹) 0.094	P¹ 2.233(2) C¹ 1.994(3) N¹ 2.166(2) H₂O 2.182(2)	P¹,C¹ 84.0 ^c C²,N ¹ 95.9 ^c P¹,N¹ 174.0 P₁O 92.7 N₁O 88.0 C_1,O 172.6	[16]
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)}. (OS(=O)₂CF₃)] (at 120 K)	or P2₁2₁2₁ 6	7.459(0) 16.565(0) 18.647(0)		PtP¹C¹N¹O (P¹C₂C¹C₃N¹) 0.051	P^1. 2.248(1) C¹ 2.005(2) N¹ 2.168(2) LO 2.249 (2)	P¹,C¹ 84.6 ^c C¹,N¹ 95.1 ^d P¹,N¹ 174.4 P₁,O 93.9 N₁,O 86.4 C₁,O 178.2	[16]
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)}. (CO)]BF₄ (at 120 K)	m P2₁/c 4	8.554(1) 15.064(3) 12.654(4)	93.03(3)	PtP¹C¹N¹C (P¹C₂C¹C₃N¹) 0.105	P^1. 2.227(2) C¹ 2.063(3) N¹ 2.158(2) OC 1.922(3)	P¹,C¹ 83.1 ^c C²_,N ¹ 88.9 ^d P¹,N¹ 172.9 P¹,C 94.4 N¹,C 94.4 C¹,C 172.3	[16]
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)}. (CH₃)] (at 120 K)	tg R-3 8	24.224(3) 17.904(4)		PtP¹C¹N¹C (P¹C₂C¹C₃N¹) 0.051	P¹ 2.204(2) C¹ 2.075(2) N¹ 2.193(2) H₃C 2.187(2)	P¹,C¹ 83.4 ^c C¹_,N ¹ 93.4 ^d P¹N¹ 177.4 P¹,C 94.0 N¹,C 89.4 C¹,C 175.2	[17]
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)}{C(Ph)=N=N)} (at 120 K)	tr P $\bar{1}$ 2	9.004(1) 10.345(2) 14.201(3)	72.53(8) 88.51(3) 77.85(3)	PtP¹C¹ N¹C (P¹C₂C¹C₃N¹) 0.158	P¹ 2.220(1) C¹ 2.053(2) N¹ 2.176(2) LC 2.146(3)	P¹,C¹ 83.6 ^c C¹,N ¹ 93.2 ^d P¹N¹ 168.0 P¹,C 96.8 N¹,C 88.4 C¹,C 169.5	[18]
[Pt{η³-Bu^t₂P(C₈H₇NEt₂)}. (Cl)] (at 120 K)	m P2₁/n 4	12.065(2) 13.391(3) 13.625(3)	104.69(3)	PtP¹C¹N¹Cl (P¹C₂C¹C₃N¹) 0.138	P¹ 2.217(1) C¹ 1.971(2) N¹ 2.191(2) Cl 2.408(1)	P¹,C¹ 83.6 ^c C¹,N ¹ 82.8 ^c P¹,N¹ 166.2 P¹,Cl 100.5 N¹,Cl 93.2 C¹,Cl 174.3	[16]
[Pt{η³-Bu^t₂P(C₉H₉NMe₂)}. (Cl)] (at 120 K)	m P2₁/c 4	16.431(3) 7.487(1) 17.060(3)	108.35(3)	PtP¹C¹N¹Cl (P¹C₂C¹C₂N¹) 0.077	P¹ 2.226(1) C¹ 2.020(2) N¹ 2.189(2) Cl 2.419(2)	P¹,C¹ 84.8 ^c C¹,N ¹ 94.4 ^d P¹,N¹ 174.2 P¹,Cl 93.9 N¹,Cl 87.2 C¹,Cl 174.8	[17]
[Pt{η³-Ph₂P(C₁₆H₁₃NMe₂)}. (Cl)] (at 103 K)	tr P $\bar{1}$ 2	9.528(0) 10.415(0) 14.436(0)	81.31(0) 74.58(0) 66.96(0)	PtP¹C¹N¹Cl (P¹C₃C¹C₂N¹) 0.066	P¹ 2.196(1) C¹ 1.992(2) N¹ 2.152(2) Cl 2.384(1)	P¹,C¹ 95.5 ^d C¹_,N ¹ 82.2 ^c P¹,N¹ 176.1 P¹,Cl 89.5 N¹,Cl 92.6 C¹,Cl 174.4	[19]
[Pt{η³-Ph₂P(C₂₃H₂₈N₃)}. (Cl)]PF₆.thf	tg 14 8	21.495(0) 19.249 (0)		PtP¹C¹N¹Cl (P¹C₃NC¹NC₃N¹) 0.074	P¹ 2.258(1) C¹ 1.991(2) N¹ 2.073(3) Cl 2.347(1)	P¹,C¹ 92.8 ^e C¹,N ¹ 86.1 ^e P¹,N¹ 178.2 P¹,Cl 93.8 N¹,Cl 87.1 C¹,Cl 171.3	[20]
[Pt{η³-Ph₂P(C₈H₆O₂NPh)}. (NCCH₃)]BF₄ (at 110 K)	m P2₁/c 4	15.601(0) 9.496(0) 21.046(0)	120.60(0)	PtP¹C¹N¹N (P¹OCC¹C₂N¹) 0.186	P¹ 2.200(2) C¹ 1.950(1) N¹ 2.127(2) N 2.066(2)	P¹,C¹ 80.3 ^c C¹,N ¹ 79.4 ^c P¹,N¹ 159.2 P¹,N 104.1 N¹,N 96.3 C¹,N ¹ 174.4	[21]
[Pt{η³-Ph₂P(C₈H₆O₂NPh)}. (Br)] (at 150 K)	or P2₁2₁2₁ 6	14.459(0) 14.757(0) 21.590(0)		PtP¹C¹N¹Br (P¹OCC¹C₂N¹) 0.156	P¹ 2.177(2) C¹ 1.946(3) N¹ 2.134(3) Br 2.488(1)	P¹,C¹ 81.0 ^c C¹,N¹ 79.0 ^c P¹,N¹ 159.9 P¹,Br 100.9 N¹,Br 99.1 C¹,Br 178.1	[21]
[Pt{η³-Prⁱ₂P(C₁₁H₁₅NO₂)}. (Br)] (at 150 K)	or Pna2₁ 6	23.138(0) 10.031(0) 8.207(0)		PtP¹C¹N¹Br (P¹OCC¹C₂N¹) 0.176	P¹ 2.180(1) C¹ 1.966(6) N¹ 2.192(5) Br 2.509(2)	P¹,C¹ 82.1(2) ^c C¹,N ¹ 79.9(2) ^c P¹,N¹ 159.4(1) P¹,Br 99.8(1) N¹,Br 97.5(1) C¹,Br 175.8(1)	[22]

Footer: ^a. The chemical identity of the coordinated atom/ligand is specified in these columns; ^b. The parameter τ4 specifies a degree of distortion; ^c. Five-membered metallocyclic ring; ^d. Six-membered metallocyclic ring; ^e. Seven-membered metallocyclic ring.

Table 3. Summary of total mean values of τ₄ and selected structure parameters of analyzed metallocycles.

Chelate Rings Membered	Σ Sums of Chelate Rings L-Pt-L/L-Pt-L°	trans α L-Pt-L°	trans β L-Pt-L°	Σ trans α+β L-Pt-L°	τ₄
5+5	167.4	163.3	174.4	337.7	0.158
5+6	176.3	172.3	174.4	346.8	0.094
6+5	177.8	175.2	173.8	349.0	0.079
7+7	178.9	178.2	171.3	349.5	0.074
6+6	183.7	176.5	175.5	352.0	0.056

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Melník, M.; Mikušová, V.; Mikuš, P. Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects. Inorganics 2023, 11, 338. https://doi.org/10.3390/inorganics11080338

AMA Style

Melník M, Mikušová V, Mikuš P. Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects. Inorganics. 2023; 11(8):338. https://doi.org/10.3390/inorganics11080338

Chicago/Turabian Style

Melník, Milan, Veronika Mikušová, and Peter Mikuš. 2023. "Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects" Inorganics 11, no. 8: 338. https://doi.org/10.3390/inorganics11080338

APA Style

Melník, M., Mikušová, V., & Mikuš, P. (2023). Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects. Inorganics, 11(8), 338. https://doi.org/10.3390/inorganics11080338

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Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects

Abstract

1. Introduction

2. Results and Discussion

2.1. Pt(η³-P¹C¹C²)(Y) Type

2.2. Pt(η³-P¹C¹N¹)(Y) Type

2.2.1. Pt(η³-P¹C¹N¹)(OL) Type

2.2.2. Pt (η^3-P¹C¹N¹)(CL) Type

2.2.3. Pt(η³-P¹C¹N¹)(Cl) Type

2.2.4. Pt(η³-P¹C¹N¹)(Y) (Y = NL, Br) Type

3. Conclusions

Author Contributions

Funding

Data Availability Statement

Acknowledgments

Conflicts of Interest

Abbreviations

References

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Heterotridentate Organomonophosphines in Pt(η3-P1C1C2)(Y) and Pt(η3-P1C1N1)(Y) Derivatives—Structural Aspects

Abstract

1. Introduction

2. Results and Discussion

2.1. Pt(η3-P1C1C2)(Y) Type

2.2. Pt(η3-P1C1N1)(Y) Type

2.2.1. Pt(η3-P1C1N1)(OL) Type

2.2.2. Pt (η3-P1C1N1)(CL) Type

2.2.3. Pt(η3-P1C1N1)(Cl) Type

2.2.4. Pt(η3-P1C1N1)(Y) (Y = NL, Br) Type

3. Conclusions

Author Contributions

Funding

Data Availability Statement

Acknowledgments

Conflicts of Interest

Abbreviations

References

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Heterotridentate Organomonophosphines in Pt(η³-P¹C¹C²)(Y) and Pt(η³-P¹C¹N¹)(Y) Derivatives—Structural Aspects

2.1. Pt(η³-P¹C¹C²)(Y) Type

2.2. Pt(η³-P¹C¹N¹)(Y) Type

2.2.1. Pt(η³-P¹C¹N¹)(OL) Type

2.2.2. Pt (η^3-P¹C¹N¹)(CL) Type

2.2.3. Pt(η³-P¹C¹N¹)(Cl) Type

2.2.4. Pt(η³-P¹C¹N¹)(Y) (Y = NL, Br) Type