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Melník, M.; Mikušová, V.; Mikuš, P. Pt(η3–P1C2X1C2P2)(Y) Derivative Types. Encyclopedia. Available online: https://encyclopedia.pub/entry/48798 (accessed on 19 May 2024).
Melník M, Mikušová V, Mikuš P. Pt(η3–P1C2X1C2P2)(Y) Derivative Types. Encyclopedia. Available at: https://encyclopedia.pub/entry/48798. Accessed May 19, 2024.
Melník, Milan, Veronika Mikušová, Peter Mikuš. "Pt(η3–P1C2X1C2P2)(Y) Derivative Types" Encyclopedia, https://encyclopedia.pub/entry/48798 (accessed May 19, 2024).
Melník, M., Mikušová, V., & Mikuš, P. (2023, September 05). Pt(η3–P1C2X1C2P2)(Y) Derivative Types. In Encyclopedia. https://encyclopedia.pub/entry/48798
Melník, Milan, et al. "Pt(η3–P1C2X1C2P2)(Y) Derivative Types." Encyclopedia. Web. 05 September, 2023.
Pt(η3–P1C2X1C2P2)(Y) Derivative Types
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This entry is adapted from the peer-reviewed paper 10.3390/cryst13091340

Structural data are classified and analyzed for almost seventy complexes of the general formula Pt(η3–P1X1P2)(Y) (X1 = O, N, C, S, Si) and (Y = various monodentate ligands), in which the respective η3–P1X1P2 ligand forms a pair of five-membered metallocyclic rings with a common X1 atom of the P1C2X1C2P2 type.

heterotridentate Pt(η3–P1C2X1C2P2)(Y) trans-influence

1. Introduction

The chemistry of platinum coordination complexes has been intensively studied and developed for more than five decades, focusing on the relationship between structure and reactivity. The chemistry of platinum is important in the fields of biochemistry [1], catalysis [2], spectroscopy [3][4], and coordination theory. Very recently, Horiuchi and Umakoshi published a review that focused on the importance of and advances in the synthetic, structural, thermodynamic, electronic, and photophysical properties of Pt-based heteropolynuclear complexes [5].
Significant attention has been paid to organomonophosphines, representing soft donor ligands in the chemistry of platinum. There are a large number of published structural studies on such complexes that have been classified and analyzed [6]. Another group of related structural studies is devoted to Pt(II) complexes with organodiphosphines [7][8]. Recently, researchers analyzed and classified structural data for the following compositions: Pt(η4–P4L), Pt(η4–P3 SiL), Pt(η4–P2N2L), Pt(η4–P2S2L), Pt(η4–P2C2L), Pt(η4–PN3L), and Pt(η4–PN2OL) [9]. As can be seen, P-donor ligands prevail by far. η4–ligands form 10-, 11-, 12-, 14-, and 16-membered metallocycles. A distorted square planar geometry around Pt(II) atoms with cis-configuration prevails by far.
From an application point of view, multifunctional ligands responsible for secondary catalyst–substrate interactions over the course of a catalytic transformation play increasingly important roles in contemporary catalysis, as has been demonstrated also within these groups of platinum complexes with P-donor ligands. Pincer-type complexes constitute a family of compounds that have recently attracted significant interest. They play important roles in organometallic reactions and mechanisms, catalysis, and the design of new materials (see, e.g., reviews [10][11][12][13][14][15][16]). The high thermal stability of such complexes, particularly those based on an aromatic backbone, permits their use as catalysts at elevated temperatures in various catalytic applications. Bulky bis-chelating pincer-type ligands are effective in the stabilization of highly unsaturated cationic complexes and the stabilization of reactive species [10][11][12][13][14][15][16][17].

2. Pt(η3–P1C2X1C2P2)(Y), (X1 = O1,N1, C1, S1, or Si1)

There are 69 complexes in which heterotridentate organodiphosphines create a pair of “equal” five-membered metallocyclic rings with a common X1 atom. These tridentate ligands with monodentate Y ligands construct a square planar geometry with various degrees of distortion around Pt(II) atoms. These complexes are centrosymmetric. Groups of X1 = O1, N1, or C1 structures, which were mentioned for several representatives in the previous work devoted to any type of n-member metallocycle rings (n = 5,6,7) but different types of atoms between P1 and X1 [18], along with a new group of X1 = S1, Si1 structures, highlighting structural aspects related to distortion.

2.1. Pt(η3–P1O1P2)(P3)

Monoclinic [Pt{η3-Ph2P(C15H12O)PPh2}{η1–P3(C5H4N)(Ph)2}](CF3SO3)2•0.5H2O [19] (at 150 K) is the only example of the P1C2O1C2P2 metallocycle type. The heterotridentate η3-P1O1P2 ligand with monodentate P3L creates a distorted square planar geometry around a Pt(II) atom.
The total mean Pt–L bond distance elongates in the following sequences:
Pt (η3-P1O1P2)(Y), Y = P3L (1 example): Pt–L: 2.189 (3) Å (O1, trans to P3) < 2.239 (2) Å (P3) < 2.302 (2,11) Å (P1,2, mutually trans)

2.2. Pt(η3–P1N1P2)(Y), (Y = N2 L, (x1), CL(x9), Cl(x7), P3L(x2))

There are nineteen examples of the P1C2N1C2P2 metallocyclic type with a common N1 atom. Monoclinic [Pt{η3-Ph2P(C12H8N)PPh2}(N2C5H5)]CF3SO3.toluene [20] is the only example in which a N2 donor ligand completed a square planar geometry around a Pt(II) atom (PtP1N1P2N2). The structure of [Pt{η3-Ph2P(C12H8N)PPh2}(N2C5H5)]+ [20] is shown in Figure 1 as an example.
Figure 1. Structure of [Pt{η3-Ph2P(C12H8N)PPh2}(py)].
In the following eight complexes, triclinic [Pt{η3-But2P(C7H7N)PBut2}(CH3)]Cl (at 100 K), monoclinic [Pt{η3-But2P(C7H6N)PBut2}(CH3)] [21] (at 100 K), monoclinic [Pt{η3-Ph2P(C7H7N)PPh2}{C(=O)Et}]BF4.(CH2Cl2)5 [22] (at 100 K), triclinic [Pt{η3-Ph2P(C7H7N)PPh2}(CH2CHO)]BF4 [22], triclinic [Pt{η3-Ph2P(C7H7N)PPh2}(CH=CHPh)]BF4 [23], monoclinic [Pt{η3-Pri2P(C12H7F2N)PPri2}(C6H4F)]B(C6H5)4 (at 110 K) and monoclinic [Pt{η3-Pri2P(C12H7F2N)PPri2}. (p-toluene)]B(C6H5)4 [24] (at 110 K), and monoclinic [Pt{η3-Ph2P(C7H7N)PPri2}(η1-C11H15NO3)]BF4 [25] and a η3-P1N1P2 ligand with a monodentate CL create a distorted square planar geometry around a Pt(II) atom (PtP1N1P2C).
There are seven complexes, monoclinic [Pt{η3-Ph2P(C12H8N)PPh2}(Cl)](C6H6)5 [20], trigonal [Pt{η3-But2P(C7H7N)PBut2}(Cl)]Cl [21], orthorhombic [Pt{η3-But2P(C7H6N)PBut2}(Cl)] [21] (at 120 K), monoclinic [Pt{η3-Pri2P(C12H6F2N)PPri2}(Cl)]CHB11Cl11 [24] (at 110 K), monoclinic [Pt{η3-Ph2P(C14H12N)PPri2}(Cl)]C6H6 [26] (at 183 K) and triclinic [Pt{η3-Ph2P(C14H12N)Pcy2}(Cl)]C6H6 [26] (at 183 K), and monoclinic [Pt{η3-Ph2P(C7H8N)PPh2}(Cl)] [27] in which Cl− anions complete inner coordinate spheres (PtP1N1P2Cl).
In the remaining two complexes, triclinic [Pt{η3-(η2-(C24H44)P(C7H6N)P(C24H44)} (PPh3)].2CH2Cl2 [28] (at 103 K) and monoclinic [Pt{η3-(η2-C18H28)P(C7H6N)P(η2-C18H29)}(P3cy3)] [29] (at 103 K), a monodentate P3L is involved (PtP1N1P2P3).
The total mean Pt-L bond distance elongates in the following sequences:
Pt (η3-P1N1P2)(Y), Y = N2L, CL, Cl, P3L (19 examples): Pt–N1: (trans to Y): 2.024 (3) Å (N2) < 2.077 (2,5) Å (P3) < 2.128 (2,70) Å (C) < 2.201 (3,26) Å (Cl); Pt–Y: (trans to N1): 2.056 (3) Å (N2) < 2.072 (2,85) Å (C) < 2.277 (2,5) Å (P3) < 2.316 (2,17) Å (Cl); Pt–P1,2: (mutually trans) is 2.287 (2,17) Å

2.3. Pt(η3–P1C1P2)(Y), (Y = OL (x4), NL(x4), C2L (x9), Cl (x12), Br (x2))

There are over thirty examples of the P1C2C1C2P2 metallocycle type. In four complexes, monoclinic [Pt{η3-(CF3)2P(C8H7)P(CF3)2}(H2O)].SbF6 [30], triclinic [Pt{η3-Ph2P(C8H7)Ph2P}(H2O)]CF3SO3 [31], triclinic [Pt{η3-Ph2P(C8H7)PPh2}(OMe)]0.5C6H6 [31], and orthorhombic [Pt{η3-Pri2P(C20H11)PPri2}(OOCCF3)] [32] (Figure 2), a monodentate OL ligand completed a square planar geometry (PtP1C1P2O).
Figure 2. Structure of [Pt{η3-Pri2P(C20H11)PPri2}(OOCCF3)].
In four complexes, monoclinic [Pt{η3-(CF3)2P(C8H7)P(CF3)2} (NC5H5)]B(C6H5)4 [30], orthorhombic [Pt{η3-Ph2P(C20H13O4)PPh2}(N≡CCH3)]BF4 [32], monoclinic [Pt{η3-Ph2P(C20H11O2)PPh2}(NC5H5)]Cl}](NC5H5) [33], and monoclinic [Pt{η3-Ph2P(C20H11O4)PPh2} (N≡CCH3)]BF4. CH2Cl2 [33], monodentate NL ligands completed the inner coordination sphere PtP1N1P2N2.
There are nine complexes, tetragonal [Pt{η3-Ph2P(C24H19O2)PPh2}(CN)] [34], triclinic [Pt{η3-(CF3)2P(C8H7)P(CF3)2}(CO)]SbF6 [35], monoclinic [Pt{η3-(CF3)2P(C8H7)P(CF3)2}(CH3)] [35], monoclinic [Pt{η3-Pri2P(C8H7)PPri2}(CO)]CF3SO3 0.5C6H6 [36], monoclinic [Pt{η3-But2P(C8H7)PBut2}(η1-CHOMe)]CF3SO3.thf [36], orthorhombic [Pt{η3-But2P(C12H9)PBut2}(CO)]BF4 [37], monoclinic [Pt{η3-Ph2P(C8H7)PPh2}(η1-C12H19N2)] [38], monoclinic [Pt{η3-Ph2P(C6H7N2)PPh2}(η1-C3F2)] [39], and monoclinic [Pt{η3-Ph2P(C8H7)PPh2}(η1-C12H21N2)]2(BF4) [40], in which a monodentate C2L ligands are involved (PtP1C1P2C2).
In twelve complexes, triclinic [Pt{η3-Ph2P(C20H11O2)PPh2}(Cl)](CH3CN)4 [33], monoclinic [Pt{η3-Ph2P(C24H19O2)PPh2}(Cl)] [34], monoclinic [Pt{η3-(CF3)2P(C8H7)P(CF3)2}(Cl)]1.5C6H14 [35], orthorhombic [Pt{η3-But2P(C8H7)PBut2}(Cl)] [36], monoclinic [Pt{η3-But2P(C12H9)PBut2}(Cl)] [37], monoclinic [Pt{η3-But2P(C8H7)PBut2}(Cl)] [41], triclinic [Pt{η3-Pri2P(C8H7)PPri2}(Cl)] [42], monoclinic [Pt{η3-Ph2P(C14H7)PPh2}(Cl)] [43], monoclinic [Pt{η3-Ph2P(C8H7)PPh2}(Cl)]CH3CN [44], orthorhombic [Pt{η3-Ph2P(C18H11O8)PPh2}(Cl)]CH3CN [44], orthorhombic [Pt{η3-Ph2P(C18H11O8)PPh2}(Cl)]CH2Cl2 [45], and monoclinic [Pt{η3-Pri2P(C20H11)PPri2}(Cl)](CH3CN)2 [46], a Cl− anion completed inner coordination spheres around each Pt(II) atom (PtP1C1P2Cl).
A Br− anion is involved in two monoclinic complexes, [Pt{η3-Ph2P(C8H7)PPh2}(Br)] [47] and [Pt{η3-But2P(C8H7)PBut2}(Br)] [48].
The total mean PL-L bond distance elongates in the following sequences:
Pt (η3-P1C1P2)(Y), Y = OL, NL, C2L Cl, Br (31 examples): Pt–C1: (trans to Y): 2.001 (3,8) Å (N) < 2.027 (2,8) Å (O) ~ 2.027 (2,6) Å (Br) < 2.031 (2,12) Å (Cl) < 2.049 (2) Å (C2); Pt–Y: (trans to C1): 2.065 (7,12) Å (C2) < 2.085 (2,12) Å (N) < 2.132 (2,9) Å (O) < 2.400 (2,16) Å (Cl) < 2.467 (1,10) Å (Br); Pt–P1,2: (mutually trans) is 2.75 (2,12) Å.

2.4. Pt(η3–P1S1P2)(Y), (Y = CH3 (x1), Cl (x2), P3Ph3 (x2), I (x1))

There are six complexes in which each heterotridentate ligand creates a P1C2S1C2P2 metallocycle. Monoclinic [Pt{η3-Ph2P(C6H4)S(=O)(C6H4)PPh2}(CH3)]PF6.CH3CN [49] (at 100 K; Figure 3) is the only example with a (PtP1S1P2C) chromophore. In monoclinic [Pt{η3-Ph2P(C6H4)S(=O)(C6H4)PPh2}(Cl)]PF6.CH3CN [49] and triclinic [Pt{η3-Ph2P(CH2)2S(=O)(CH2)2PPh2}(Cl)]ClO4 [50], the Cl− anion completed a square planar geometry (PtP1S1P2Cl).
Figure 3. Structure of [Pt{η3-Ph2P(C6H4)S(=O)(C6H4)PPh2}(CH3)].
In triclinic [Pt{η3-Ph2P(C6H4)S(=O)(C6H4)PPh2}(P3Ph3)]0.5.CH2Cl [49] (at 100 K) and orthorhombic [Pt{η3-Ph2P(CH2)2S(CH2)2PPh2}(P3Ph3)]ClO4 [51] (at 100 K), the P3Ph3 are involved (PtP1S1P2P3).
In another triclinic [Pt{η3-Ph2P(C23H28S)PPh2}(I)].1.74 CH2Cl2 [52] (at 150 K), the I− anion is involved (PtP1S1P2I).
The total mean PL-L bond distance elongates in the sequences:
Pt (η3-P1S1P2)(Y), Y = CL, Cl, P3L, I (6 examples): Pt–S1: (trans to Y): 2.187 (2,5) Å (Cl) < 2.256 (2) Å (I) < 2.268 (2) Å (C) < 2.328 (2,15) Å (P3); Pt–Y: (trans to S1): 2.093 (2) Å (C) < 2.285 (2,3) Å (P3) < 2.317 (2,5) Å (Cl) < 2.510 (1) Å (I); Pt–P1,2: (mutually trans) is 2.300 (4,30) Å.

2.5. Pt(η3–P1Si1P2)(Y), (Y = H (x2), OL (x1), NL (x1), CL (x1), Cl (x5), P3L (x1))

There are fourteen complexes in which each heterotridentate ligand creates a pair of “equal” five-membered metallocyclic rings with a common Si1 atom of the P1C2Si1C2P2 type. In two monoclinic [Pt{η3-cy2P(C6H4)Si(Me)(C6H4)Pcy2}(H)].0.5 pentane [53] (at 150 K) and [Pt{η3-cy2P(C6H4)Si(Me)(C6H4)Pcy2}(H)].1.25 pentane [53] (at 93 K), hydride completed a square planar geometry (PtP1Si1P2H).
Triclinic [Pt{η3-Ph2P(C6H4)Si(Me)(C6H4)PPh2}(OEt2)]{B(C6F5)3 (CH2Ph)}.OEt2 [54] (Figure 4) is the only example with a monodentate OEt2 ligand (PtP1Si1P2O).
Figure 4. Structure of [Pt{η3-Ph2P(C6H4)Si(Me)(C6H4)PPh2}(OEt2)].
In another triclinic [Pt{η3-Pri2P1(C6H4)Si1(C6H4PPri2)(C6H4)P2Pri2}(NC5H5)]B(C8H3F6)4 [55] (at 100 K), a monodentate NC5H5 is involved (PtP1Si1P2N).
In the following four complexes: triclinic [Pt{η3-cy2P(C6H4)Si(Me)(C6H4)Pcy2}(Ph)]OEt2 [54] (at 173 K), triclinic [Pt{η3-Ph2P(C6H4)Si(Me)(C6H4)PPh2}(CH2Ph)]CH2Cl2 [54] (at 193 K), triclinic [Pt{η3-Pri2P)(C6H4)Si(OH)(C6H4)PPri2)}(CO)]B(C6F5)4 [56] (at 120 K), and orthorhombic [Pt{η3-Pri2P(C6H4)Si(H)(C6H4)PPri2}(mes)] [57] (at 110 K), monodentate CL ligands are involved (PtP1Si1P2C).
In the following five complexes: monoclinic [Pt{η3-Ph2P(C6H4)Si(Me)(C6H4)PPh2}(Cl)] [54] (at173 K), orthorhombic [Pt{η3-Ph2P(C6H4)Si(Me)(C6H4)PPh2}(ClAlCl3)](C6H5F)2 [54] (at 193 K), monoclinic [Pt{η3-Pri2P(C6H4)Si(OH)(C6H4)PPri2}(Cl)] [56] (at 120 K), monoclinic [Pt{η3-Pri2P(C6H4)Si(H)(C6H4)Pcy2}(Cl)] [57] (at 110 K), and monoclinic [Pt{η3-cy2P(C6H4)Si(Me)(C6H4)Pcy2}(Cl)] [58] (at 110 K), tridentate P1Si1P2 with Cl− anions construct inner coordination spheres around each Pt(II) atom (PtP1Si1P2Cl).
The total mean PL-L bond distance elongates in the following sequences:
Pt (η3-P1Si1P2)(Y), Y = H, OL, NL, CL, Cl, P3L (19 examples): Pt–Si1: (trans to Y): 2.276 (2) Å (O) < 2.279 (2,6) Å (Cl) < 2.315 (2) Å (N) < 2.331 (2,5) Å (H) < 2.339 (2,17) Å (C) < 2.369 (2) Å (P3); Pt–Y: 1.51 (1,2) Å (H) < 2.122 (2,6) Å (C) < 2.222 (2) Å (N) < 2.282 (2) Å (O) < 2.316 (2) Å (P3) < 2.451 (2,13) Å (Cl); Pt–P1,2: (mutually trans) is 2.289 (2,32) Å.
The structure of monoclinic [Pt{η3-Ph2P1(C6H4)Si1(Me)(C6H4)P2Ph2}(P3Ph3)] [59] (at 123 K) is shown in Figure 5. In a distorted trigonal–pyramidal geometry, three P atoms construct a trigonal plane, and the Si1 atom occupies a pyramid. The heterotridentate P1Si1P2 ligand forms a pair of “equal” five-membered metallocyclic rings with a common Si1 atom of the P1C2Si1C2P2 type, with the mean P1–Pt–Si1/Si1–Pt–P2 bite angles of 83.3 (1,8)°. The values for the remaining angles are 120.7 (2)° (P1–Pt–P2), 119.6 (2,2.4)° (P1–Pt–P3/P3–Pt–P2), and 108.9 (2)° (Si1–Pt–P3). The Pt-L bond distance elongates in the following order: 2.290 (2.11) Å (Pt–P1, Pt–P2) < 2.318 (2) Å (Pt–P3) < 2.369 (2) Å (Pt–Si1). This is the only example of such geometries.
Figure 5. Structure of [Pt{η3-Ph2P(C6H4)Si(Me)(C6H4)PPh2}(PPh3)].

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Subjects: Crystallography
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Milan Melník
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Veronika Mikušová
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Peter Mikuš
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Update Date: 05 Sep 2023
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