Triply Bonded Galliumâ¡Phosphorus Molecules: Theoretical Designs

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Triply Bonded Gallium#Phosphorus Molecules: Theoretical Designs and Characterization Jia-Syun Lu, Ming-Chung Yang, and Ming-Der Su J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b04659 • Publication Date (Web): 16 Aug 2017 Downloaded from http://pubs.acs.org on August 17, 2017

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The Journal of Physical Chemistry

Triply Bonded Gallium≡Phosphorus Molecules: Theoretical Designs and Characterization 1

1

1,2

Jia-Syun Lu, Ming-Chung Yang, and Ming-Der Su * 1

Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan 2 Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 80708, Taiwan

*E-mail: [email protected] Abstract The effect of substitution on the potential energy surfaces of triple-bonded RGa≡PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt (C6H2-2,4,6{CH(SiMe3)2}3), and Ar* (C6H3-2,6-(C6H2-2,4,6-i-Pr3)2)) compounds was theoretically examined by using the density functional theory (i.e., M06-2X/Def2TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp). The theoretical evidences strongly suggest all of the triple-bonded RGa≡PR species prefer to select a bent form with an angle (∠Ga−P−R) of about 90°. Moreover, the theoretical observations indicate only the bulkier substituents, in particular for the strong donating groups (e.g., SiMe(SitBu3)2 and SiiPrDis2) can efficiently stabilize the Ga≡P triple bond. In addition, the bonding analyses (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) reveal that the bonding characters of such triple-bonded RGa≡PR molecules should be regarded as R´Ga

PR´. In other words, the Ga≡P triple

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bond involves one traditional σ bond, one traditional π bond, and one donoracceptor π bond. Accordingly, the theoretical conclusions strongly suggest the Ga≡P triple bond in such an acetylene analogues (RGa≡PR) should be very weak.


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I. Introduction During the past two decades, the synthetic chemistry concerning one or two carbon atoms in triply-bonded acetylene is replaced by the heavy group 14 elements E14 (= Si, Ge, Sn, and Pb) has attracted intense interest by many laboratories due to their unique structures, bonding properties as well as potential 1-23

applications.

In contrast, little information is available about both geometrical

structures and chemical behaviors of heavier acetylene analogues, RE13≡E15R (E13 and E15 are group 13 and 15 elements, respectively).

24-28

In this work, it is

our goal to investigate the possible existence of kinetic stable triply bonded RE13≡E15R species under the appropriate substutents from the theoretical viewpoints. Recently, there is a growing interest in the chemistry of molecules containing bonds between the group 13 and 15 atoms. The reason for this is due to their potential as useful precursors to semiconductors such as GaAs, InP, and 29

GaP.

In particular, owing to its low cost, good optical properties, and good

performance, GaP is familiarly found in semiconductor devices such as long wavelength detectors and semiconductor lasers, light emitting diodes (LEDs), as well as new applications such as, for instance, a host material for diluted magnetic 30-42

semiconductors.

In fact, as far as the authors are aware, a handful of

experimental information on the Ga−P single-bonded and the Ga=P double43-50

bonded molecules have been reported.

Nevertheless, no similar Ga≡P triply

bonded compound has been detected so far. This raises our interest to design theoretically the kinetically stable acetylene analogues, RGa≡PR, since RGa≡PR is isoelectronic to HC≡CH from the valence electrons’ viewpoints. 3 Environment ACS Paragon Plus


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Scheme 1. Four bulky ligands are used in this work. They are as follows: SiMe(SitBu3)2, SiiPrDis2, Tbt (C6H2-2,4,6-{CH(SiMe3)2}3), and Ar* (C6H3-2,6-(C6H2-2,4,6-i-Pr3)2).

To achieve this goal, two kinds of substituents have been used in the present work. One is the small substituents, which includes F, OH, H, CH3, and SiH3. The other is the bulky substituents, which contains SiMe(SitBu3)2, SiiPrDis2, Tbt 51-53

(C6H2-2,4,6-{CH(SiMe3)2}3), and Ar* (C6H3-2,6-(C6H2-2,4,6-i-Pr3)2).

See

Scheme 1. Moreover, in order to obtain the reasonable accuracy, three kinds of density functional theory (DFT) have been utilized to calculate their structures as well as the potential energy surfaces. They are M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp levels of theory. 4 Environment ACS Paragon Plus

54

In particular,

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it has recently reported that non-valent interactions, e.g., the London dispersion, play a prominent role on the chemical and physical properties of sterically crowded organometallic and inorganic molecules.

55

Theoretical calculations were

thus performed using the dispersion-corrected M06-2X method.

56

It is hoped that

the present study can open up a new area for studying the triply bonded RGa≡PR species. II. General Considerations In order to explain the bonding characters of the substituted triply bonded RGa≡PR molecules studied in this work (see below), we develop a simple valence-electron bonding model to interpret the bonding natures. For simplicity, one RGa≡PR molecule is firstly divided into two fragments, i.e., one R−Ga and one R−P. As a result, the valence electrons of R−Ga and R−P have two and four, respectively. As schematically shown in Figure 1, two kinds of valence-electron bonding models (model [1] and model [2]) are represented. Since all our calculated results shown below reveal that the ground states of the two 1

fragments are respectively singlet for R−Ga ([R−Ga] ) and triplet for R−P 3

1

1

1

([R−P] ). Therefore, model [1] is regarded as [R−Ga] + [R−P] → [RGa≡PR] , 3

3

1

while model [2] is represented as [R−Ga] + [R−P] → [RGa≡PR] . On the one hand, if the promotion energy (∆E1) from the ground state to the excited state for R−Ga is larger than that for R−P, then the explanations about the bonding characters of RGa≡PR should choose model [1]. On the other hand, if the excitation energy (∆E2) from the ground state to the excited state for R−P is larger than that for R−Ga, then the interpretations concerning the bonding constitutions 5 Environment ACS Paragon Plus


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of RGa≡PR should adopt model [2].

Figure 1. The valence-bond bonding models [1] and [2] for the triply bonded RGa≡PR molecule

Bearing the above bonding models in mind, we shall use the above bonding analysis to explain the geometrical structures and the bonding properties in the latter sections. III. Results and Discussion (1) Small Ligands on Substituted RGa≡PR


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In the beginning, three kinds of computational methods based on the density functional theory (DFT) have been used to investigate the properties of the triply bonded RGa≡PR compounds bearing the small groups (R). They are M062X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp levels of theory. Five small substituents (R) including F, OH, H, CH3, and SiH3 are used in this work. The 1,2-substituent-shift reactions have been utilized to examine the relative stability of the triply bonded RGa≡PR species and its corresponding doubly bonded isomers, i.e., R2Ga=P: and :Ga=PR2. That is to say, RGa≡PR → TS1 → R2Ga=P: and RGa≡PR → TS2 → :Ga=PR2. Their calculated potential energy surfaces are thus given in Figure 2. As one can see in Figure 2, three DFT computational results all demonstrate that despite any kinds of small substituents are selected, the triply bonded RGa≡PR molecules are neither kinetic nor thermodynamical stable on the 1,2-shifted potential energy surfaces since they readily migrate to the corresponding doubly bonded either R2Ga=P: or :Ga=PR2 isomers. In other words, our theoretical observations predict that experimental observations of RGa≡PR possessing the small ligands are hardly likely even in the low-temperature matrices.



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Figure 2. The Relative Gibbs free energy surfaces for RGa≡PR (R = F, OH, H, CH3, and SiH3). These energies are in kcal/mol and are calculated at the

M06-2X/Def2-TZVP,

B3PW91/Def2-TZVP,

and

B3LYP/LANL2DZ+dp levels of theory. For details see the text and Table 1. 8 Environment ACS Paragon Plus

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Table 1 The important geometrical parameters, the natural charge densities (QGa and QP), the singlet−triplet energy splittings for Ga−R and P−R units (∆EGa and ∆EP), the HOMO-LUMO energy gaps, the binding energies (BE), and the Wiberg bond index (WBI) for RGa≡PR using the M06-2X/Def2-TZVP, B3PW91/Def2-TZVP (in round brackets) and B3LYP/LANL2DZ+dp (in square brackets) levels of theory. R

F

OH

H

CH3

SiH3

GaαP (Å)

2.234 (2.216) [2.223]

2.247 (2.253) [2.266]

2.136 (2.130) [2.165]

2.155 (2.144) [2.181]

2.158 (2.147) [2.169]

R−Ga−P (°)

178.1 (179.0) [177.2]

178.9 (177.5) [177.4]

177.0 (179.5) [179.0]

172.1 (170.5) [170.3]

179.3 (179.2) [179.8]

Ga−P−R (°)

97.11 (97.68) [96.22]

98.60 (95.63) [98.20]

79.30 (82.82) [83.60]

102.3 (103.9) [103.3]

76.72 (76.67) [80.42]

R−P−Ga−R (°)

180.0 (180.0) [180.0]

180.0 (175.9) [176.8]

180.0 (180.0) [180.0]

179.9 (179.3) [177.7]

176.3 (175.7) [178.5]

1.2882 (1.1920) [1.3047]

1.2376 (1.1264) [1.2622]

0.9975 (0.9022) [1.0179]

1.1967 (1.0900) [1.2059]

0.8011 (0.6911) [0.8254]

(2) QP

0.0484 (0.0827) [0.0404]

−0.0433 −0.6674 −0.4446 −0.7249 (−0.0068) (−0.6250) (−0.3888) (−0.6525) [−0.0529] [−0.6371] [−0.4312] [−0.7214]

∆EGa for Ga−R (3) (kcal/mol)

89.37 (89.46) [86.70]

78.19 (77.73) [82.71]

46.67 (46.80) [45.66]

49.53 (48.32) [47.83]

32.94 (33.90) [37.96]

∆EP for P−R (4) (kcal/mol)

−28.91 (−33.35) [−31.76]

−17.53 (−21.29) [−20.24]

−30.75 (−35.49) [−33.16]

−26.43 (−30.26) [−29.21]

−5.804 (−8.678) [−14.46]

QGa

(1)



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HOMO − LUMO (kcal/mol) (5)

BE (kcal/mol)

WBI

(6)

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173.1 (189.0) [202.0]

162.0 (166.6) [170.0]

275.9 (227.7) [228.0]

152.8 (147.5) [150.8]

172.2 (178.5) [170.7]

98.94 (89.46) [97.14]

95.44 (91.73) [94.15]

99.16 (97.80) [93.76]

90.60 (88.40) [89.26]

96.97 (95.25) [95.31]

1.502 (1.517) [1.502]

1.503 (1.516) [1.499]

1.667 (1.700) [1.683]

1.610 (1.645) [1.643]

1.521 (1.552) [1.564]

(1) The natural charge density on the gallium atom. (2) The natural charge density on the phosphorus atom. (3) ∆EGa = E(triplet state for Ga−R) – E(singlet state for Ga−R). (4) ∆EP = E(triplet state for P−R) – E(singlet state for P−R). (5) BE = E(singlet state for Ga−R) + E(triplet state for P−R) – E(singlet state for RGa≡PR). (6) The Wiberg bond index (WBI) for the Ga≡P bond: see reference (63). Although the above calculations indicate that the triply bonded RGa≡PR molecules featuring the small substituents are instant intermediates on the 1,2migrated reaction energy surfaces, which could be very difficult to be detected in the laboratory, it is still necessary to discuss their several physical properties from the theoretical viewpoints in order to be more convenient to prepare and produce the more stable RGa≡PR species. Several selected physical properties of RGa≡PR based on three kinds of DFT calculations are listed in Table 1. As seen in Table 1, the Ga≡P triple bond distances (Å) are predicted to be in the range of 2.136−2.247 (M06-2X/Def2-TZVP), 2.130−2.253 (B3PW91/Def2-TZVP), and 2.165−2.266 (B3LYP/LANL2DZ+dp). Our anticipated triple bond lengths are somewhat larger


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than one theoretically calculated data (2.020 ± 0.0025 Å in HGa≡PH)) reported by 57

Hoffmann and co-workers.

Scheme 2. The theoretically predicted conformation for the triply bonded RGa≡PR molecule possessing the small ligands.

Interestingly, our DFT results collected in Table 1 indicate that all the R−Ga−P and Ga−P−R bond angles are predicted to be about 180.0° and 90.0°, respectively. The reason why the phosphine fragment assumes a vertical geometry 58-61

is attributed to relativistic effects.

Since phosphine belongs to the heavy

element, its valence s orbital is more contracted than its valence p orbitals. According to the so-called “orbital non-hybridization effect” or the “inert s-pair 58-61

effect”,

the valence s and p orbitals of phosphine would overlap less to form

strong hybrid orbitals. Consequently, the phosphine fragment prefers to adopt the perpendicular geometry as schematically shown in Scheme 2. Also, the DFT calculations show that all the RGa≡PR species are a planar structure and their dihedral angles R−Ga−P−R are about 180.0°. These theoretical predictions are



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quite similar to the previously calculated results mentioned by Hoffmann and co57

workers.

From Table 1, it is found that the singlet−triplet energy splitting (∆EST) of R−Ga and R−P moieties are anticipated to be about more than 33 kcal/mol and less than −5 kcal/mol, respectively. These data strongly suggest that the bonding scheme of the triply bonded RGa≡PR molecule possessing the small ligands prefers to select model [1] as schematically represented in Figure 1. That is, its Ga≡P triple bond contains one donor-acceptor σ bond and two donor-acceptor π bonds, which can be depicted as RGa

PR. Nevertheless, it is noteworthy that

there exist two factors to affect the bonding strength of its Ga≡P triple bond. One is that the lone pair orbitals of both R−Ga and R−P units include the valence s characters, which can greatly reduce the bonding strength between Ga and P atoms. The other is that the atomic radii of both Ga and P elements are quite different, in which their atomic radii (pm) are reported to be 126 and 106, respectively.

62

Again, such a difference in atomic radii can largely decrease the overlap populations between Ga and P atoms. As a consequence, from these theoretical analyses, one may readily envision that the bond order of the Ga−P bond should be very weak. Indeed, the Wiberg bond index (WBI)

63-65

given in Table 1 reveal

that the bond orders for these RGa≡PR molecules bearing the small substituents are all less than 2.0. These theoretical results strongly suggest that the RGa≡PR compounds with small ligands do not have the real triple bond, since the WBI for the C≡C bond in acetylene was calculated to be 2.99. We thus turn to choose the 12 Environment ACS Paragon Plus

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large substituents in order to search for the triply bonded RGa≡PR molecules with kinetic stability in the next section. (2) Large Ligands on Substituted R´Ga≡PR´ In this section, we chose three bulky ligands (R´), containing SiMe(SitBu3)2, SiiPrDis2, Tbt (C6H2-2,4,6-{CH(SiMe3)2}3), and Ar* (C6H3-2,6-(C6H2-2,4,6-i34

Pr3)2),

(Scheme 1) to seek the stable R´Ga≡PR´ molecules from the kinetic 55,56

viewpoints. The dispersion-corrected M06-2X/Def2-TZVP level of theory

was used to calculate the relative reaction enthalpies between the triply bonded R´Ga≡PR´ compound and its corresponding doubly bonded isomers, i.e., R´2Ga=P: and :Ga=PR´2. See Scheme 3. The computational results are collected in Table 2. From the reaction enthalpies (∆H1 and ∆H2) shown in Scheme 3 and Table 2, it is evident that regardless of bulky ligands’ choosing, the energy of R´Ga≡PR´ is always much lower than those of its corresponding isomers. The reason for such phenomena can be easily understood from the steric effect viewpoints. Accordingly, our theoretical evidences demonstrate that utilizing the sterically congested ligands can kinetically stabilize the triply bonded R´Ga≡PR´ molecules.



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Scheme 3. The relative potential energy surfaces for the triply bonded RGa≡PR molecule possessing the bulky ligands.

We also used the same level of theory to examine the physical properties of the three bulkily substituted R´Ga≡PR´ molecules, whose calculated results are collected in Table 2. As seen in Table 2, the Ga≡P triple bond distance in these substituted R´Ga≡PR´ compounds are predicted to be 2.183−2.146 Å, in comparison to one computational value (2.020 ± 0.0025 Å in HGa≡PH)) reported by Hoffmann et al.

38

Similar to the cases of the RGa≡PR species bearing the small

ligands, the DFT results shown in Table 2 demonstrate that the bulkily substituted R´Ga≡PR´ molecules also possess the bent form ( R´−Ga−P ≈ 150° and Ga−P−R´ ≈ 100°) and the trans geometry (∠R´−Ga−P−R´ ≈ 180°).

Table 2 The bond lengths (Å), bond angels (°), natural charge densities (QGa′ and QP′), singlet−triplet energy splittings for Ga−R′ and P−R′ units (∆EGa′ and ∆EP′), 14 Environment ACS Paragon Plus

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binding energies (BE), the HOMO-LUMO energy gaps, the Wiberg bond index (WBI), and some reaction enthalpies for R′Ga≡PR′ at the dispersion-corrected M06-2X/Def2-TZVP level of theory. See also Scheme 3. SiMe(SitBu3)2 SiiPrDis2

R′

Tbt

Ar*

Ga≡P (Å)

2.167

2.146

2.172

2.183

∠R′′-Ga-P (°)

158.2

161.3

152.0

158.4

∠Ga-P-R′′ (°)

127.8

120.4

117.3

126.1

∠R′′-Ga-P-R′′ (°)

176.0

175.5

169.4

166.9

(1)

0.8023

0.8266

0.8952

0.9003

(2)

−0.7655

−0.7473

−0.8662

−0.8825

30.71

31.34

34.08

38.35

−23.10

−27.47

−23.51

−20.52

83.14

81.83

73.50

71.34

QGa′ QP′

∆EGa′ for Ga-R′′ (kcal/mol) (3)

∆EP′ for P-R′′ (kcal/mol) HOMO − LUMO (kcal/mol)

(4)

BE (kcal/mol)

(5)

91.53

102.9

85.34

89.46

∆H1 (kcal/mol)

(6)

89.11

94.82

86.31

98.94

∆H2 (kcal/mol)

(6)

86.43

85.91

88.53

84.08

2.228

2.235

2.017

2.114

WBI

(7)

(1) The natural charge density on the gallium atom. (2) The natural charge -1

density on the phosphorus atom. (3) ∆EGa′ (kcal mol ) = E(triplet state for -1

Ga−R′) – E(singlet state for Ga−R′). (4) ∆EP′ (kcal mol ) = E(triplet state for -1

P−R′) – E(singlet state for P−R′). (5) BE (kcal mol ) = E(triplet state for Ga−R′) + E(triplet state for P−R′) – E(singlet for R′Ga≡PR′). (6) See Scheme 3. (7) The Wiberg bond index (WBI) for the GaαP bond: see reference (63). 15 Environment ACS Paragon Plus


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Besides these, the ∆EST values given in Table 2 indicate that all the R´−Ga and R´−P moieties have the singlet ground state and triplet ground state, respectively. In particular, Table 2 shows that the modulus ∆EGa′ and ∆EP′ for the R´−Ga and R´−P units are respectively estimated to larger than 30 kcal/mol and 20 kcal/mol, respectively. The absolute values of the ∆EGa′ gaps for R´−Ga are still larger than the ∆EP′ for R´−P. However, the differences between these absolute values of the ∆EST are lower than those in the RGa≡PR molecules with small R groups. Therefore, one can expect that the bonding natures of the triply bonded R´Ga≡PR´ compounds featuring the bulkier groups have a greater tendency toward model [2]. Therefore, according to demonstrations in Figure 1, the Ga≡P triple bond in the bulkily substituted R´Ga≡PR´ molecules encompass one covalent σ bond, one covalent π bond, and one donor-acceptor π bond, which can be described as R´Ga

PR´. As mentioned earlier, due to the fact that atomic

radii of Ga and P are quite different (126 and 106, respectively)

62

and the lone pair

orbitals of both fragments involve the s character rather than the pure p orbitals, one may thus anticipate that the bond strength of the Ga≡P triple bond should be very weak. Indeed, the theoretically supporting data given in Table 2 confirm this prediction. Further, the introduced charge decomposition analysis (CDA), which was 66

reported by Dapprich and Frenking,

is a method for analyzing donor-acceptor

interactions of a complex X−Y in terms of donation X→Y, back-donation X←Y, and repulsive polarization X↔Y. We thus use the CDA method to interpret the two

components

(i.e.,

R′−Ga

and

R′−P)

interactions


in

terms

of

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ts, whose computational results concerning 67

the (SiMe(SitBu3)2)−Ga≡P−(SiMe(SitBu3)2) system are collected in Table 3.

It

can be seen in Table 3 that the largest contributions to Y term is No.270 (HOMO−1) orbital, indicating that a R′−P unit donates electrons to a R′−Ga monomer mainly through the HOMO−1 orbital. Also, it can be seen from Table 3 that the largest contributions to Y term is No.271 (HOMO) orbital, implying that a R′−P moiety donates electrons to a R′−Ga component principally through the HOMO orbital. According to the computational results shown in Table 3, the net amount of electron transfer (i.e., the (X-Y) term) is negative (−0.123), suggesting that the R′−P fragment donates more electrons to the R′−Ga fragment, which is consistent with the valence-electron bonding model (Figure 1; model [2]). That is to say, again, the bonding nature of R′Ga≡PR′ can be represented as R′Ga

PR′.

Table 3 The charge decomposition analysis (CDA) results(a) for R′Ga≡PR′ (R′ = SiMe(SitBu3)2) system based on M06-2X orbitals, where X term indicates the number of electrons donated from R′−Ga fragment to R′−P fragment, Y term indicates the number of electrons back donated from R′−P fragment to R′−Ga fragment and W term indicates the number of electrons involved in repulsive polarization. Significant X and Y terms are bolded for easier comparison. Orbital

Occupancy

X

Y

X−Y

W

261

2.000000

0.000071

-0.000081

0.000152

-0.000354



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 31

262

2.000000

0.003716

0.001975

0.001741

-0.035863

263

2.000000

0.000062

0.001908

-0.001846

-0.002735

264

2.000000

0.000143

0.000297

-0.000153

-0.000254

265

2.000000

-0.000100

0.000764

-0.000864

-0.000869

266

2.000000

0.000376

0.001766

-0.001390

-0.003342

267

2.000000

0.001717

-0.000580

0.002296

-0.004205

268

2.000000

0.000356

0.001232

-0.000875

0.008302

269

2.000000

0.011375

0.032222

-0.020847

-0.014361

270

2.000000

0.040273

0.048253

-0.007980

-0.025791

HOMO

271

2.000000

0.029049

0.069794

-0.040744

-0.118032

LUMO

272

0.000000

0.000000

0.000000

0.000000

0.000000

273

0.000000

0.000000

0.000000

0.000000

0.000000

542.0000

0.124740

0.247616

-0.122876

-0.012634

sum(b) (a)

For clearness, only list the X, Y, and W terms for HOMO(No.271)−10 ~

LUMO+2.

(b)

Summation of contributions from all unoccupied and occupied

orbitals.

Table 4 The natural bond orbital (NBO) and the natural resonance theory (NRT) analysis for R′′Ga≡PR′′ molecules that feature ligands (R′ = SiMe(SitBu3)2, SiiPrDis2, and Tbt (C6H2-2,4,6-{CH(SiMe3)2}3), and Ar* (C6H3-2,6-(C6H2-2,4,6-i-Pr3)2)) at the dispersion-corrected M06-2X/Def2-TZVP level of theory.

(1,2)

NBO Analysis R'Ga≡PR'

WBI

Occupancy σ: 1.92

R' = 2.23 SiMe(SitBu3)2

π⊥: 1.86 π‖: 1.88

R' = SiiPrDis2 2.24

σ: 1.94

Hybridization

NRT Analysis Polarization

total / covalent / ionic

22.98% (Ga) 77.13% (P) 19.24% (Ga) 3.51 5.28 2.14/1.25/0.89 π⊥: 0.4387 Ga (sp ) + 0.8987 P (sp ) 80.76% (P) 16.07% (Ga) π‖: 0.4009 Ga (sp99.99) + 0.9161 P (sp99.99) 83.93% (P) 24.94% (Ga) 1.76 0.93 σ: 0.4994 Ga (sp ) + 0.8664 P (sp ) 2.77/1.03/1.74 75.06% (P)

Resonance weight

σ: 0.4782 Ga (sp1.77) + 0.8783 P (sp0.96)


Ga−P : 11.52% Ga=P : 72.62% Ga≡P : 15.86%

Ga−P : 6.99%

Page 19 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


R' = Tbt

R' = Ar*

2.02

2.11

(1)

π⊥: 1.89

π⊥: 0.4579 Ga (sp3.82) + 0.8890 P (sp9.07)

π‖: 1.93

π‖: 0.4506 Ga (sp99.99) + 0.8927 P (sp1.00)

σ: 1.88

σ: 0.6283 Ga (sp1.14) + 0.7779 P (sp20.45)

π⊥: 1.89

π⊥: 0.4446 Ga (sp15.60) + 0.8957 P (sp99.99)

π‖: 1.91

π‖: 0.4255 Ga (sp99.99) + 0.8831 P (sp99.99)

σ: 1.88

σ: 0.6417 Ga (sp0.99) + 0.7670 P (sp18.35)

π⊥: 1.87

π⊥: 0.4427 Ga (sp46.19) + 0.8967 P (sp99.99)

π‖: 1.90

π‖: 0.4249 Ga (sp99.99) + 0.8722 P (sp1.00)

20.97% (Ga) 79.03% (P) 20.30% (Ga) 79.70% (P) 39.48% (Ga) 60.52% (P) 19.77% (Ga) 1.93/1.09/0.84 80.23% (P) 18.10% (Ga) 81.90% (P) 41.17% (Ga) 58.83% (P) 19.60% (Ga) 2.05/1.62/0.43 80.40% (P) 18.05% (Ga) 81.95% (P)

Ga=P : 83.99% Ga≡P : 9.02%

Ga−P : 18.19% Ga=P : 70.12% Ga≡P : 11.69%

Ga−P : 15.94% Ga=P : 74.11% Ga≡P : 9.95%

The value of the Wiberg bond index (WBI) for the Ga≡P bond and

the occupancy of the corresponding σ and π bonding NBO (see reference (41)). (2) NRT; see references (68-70). In order to gain more understanding about the bonding properties of the triply bonded R´Ga≡PR´ with bulkier ligands, the natural resonance theory 68-70

(NRT)

have been used to analyze their electron densities. The computational

results based on the dispersion-corrected M06-2X/Def2-TZVP method are collected in Table 4. In the case of (SiMe(SitBu3)2)−Ga≡P−(SiMe(SitBu3)2), for instance, Table 4 reveals that a combined weight of triply bonded resonance structures of 15.9 %, which leads to an NRT Ga≡P bond order of 2.14. The Ga≡P triple bond of SiMe(SitBu3)2)−Ga≡P−(SiMe(SitBu3)2 has considerable covalent character, as signed by the higher covalent part of the NRT bond order (1.25) than the ionic part (0.89). Further evidence into the electronic structure of SiMe(SitBu3)2)−Ga≡P−(SiMe(SitBu3)2 was supplied by a NBO analysis of the electron density. From Table 4, it indicates that three localized neutral bond orbitals corresponding to one σ and two π (π⊥ and π‖) components of the Ga≡P



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 31

triple bond. In particular, the DFT calculations demonstrate that its σ bond is polarized towards the phosphine element (77.1 %) and the two π-bonds are again strongly polarized towards the phosphine element (80.8 % and 83.9 %). Additionally,

the

optimized

wave

functions

of

(SiMe(SitBu3)2)−Ga≡P−(SiMe(SitBu3)2) illustrating the Ga≡P π bonding orbitals are collected in Figures 3(a) and 3(b). The similar bonding schemes for the other three triply bonded molecules are also given in Supporting Information.

(a) π⊥

(b) π‖ Figure 3: The

natural

Ga≡P

π

bonding

orbitals

((a)

and

(SiMe(SitBu3)2)−Ga≡P−(SiMe(SitBu3)2. Also see Figure 1. IV. Conclusion


(b))

for

Page 21 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


In this work, we have used both small and bulky ligands to study the effects of substituents on the triply bonded RGa≡PR molecules in order to find out the stable compounds from the theoretical viewpoints, from which experimental chemists can easily design and synthesize such molecules with a Ga≡P triple bond. The present theoretical studies reveal that small substituents, regardless of electronegativity or electropositivity, cannot efficiently stabilize the triply bonded RGa≡PR compounds. Only the bulkier substituents can greatly stabilize the RGaPR species featuring a Ga≡P triple bond due to the steric overcrowding properties of bulky substituents. Our bonding analyses, including NBO and NRT, demonstrate that the bonding characters of such bulkily substituted R´Ga≡PR´ species can be depicted as R´Ga

PR´. In addition, according to the theoretical

analyses (i.e., NBO, NRT, and CDA) presented in this work, which can be easily understood from the valence-bond bonding model (Figure 1), one may readily envision that the Ga≡P triple bond in such R´Ga≡PR´ molecules should be very weak, owing to the poor overlap populations between gallium and phosphorus elements. These predictions may serve as a guide to future synthetic efforts and to indicate problems that merit further study by both theory and experiment, which should be helpful for further developments in RE13≡E15R chemistry. Acknowledgments The authors are grateful to the National Center for High-Performance Computing of Taiwan for generous amounts of computing time, and the Ministry



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Page 22 of 31

of Science and Technology of Taiwan for the financial support. Special thanks are also due to reviewers 1, 2, and 3 for very help suggestions and comments. Supporting Information Available: The optimized geometries for the various points of RGa≡PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt, and Ar*)

at

the

M06-2X/Def2-TZVP,

B3PW91/Def2-TZVP

and

B3LYP/LANL2DZ+dp levels of theory. This material is available free of charge via the Internet at http://pubs.acs.org.


Page 23 of 31

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References: (1)

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(2)

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(3)

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Seidu, I.; Seth, M.; Ziegler, T. Role Played by Isopropyl Substituents in Stabilizing the Putative Triple Bond in Ar′EEAr′ [E = Si, Ge, Sn; Ar′ = C6H3-2,6-(C6H3-2,6-Pri2)2] and Ar*PbPbAr* [Ar* = C6H3-2,6-(C6H2-2,4,6Pri3)2]. Inorg. Chem. 2013, 52, 8378-8388.

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(6)

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(7)

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(8)

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(9)

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(CabC,N). X-ray Structures of (CabC,N)SnR2X (R = Me, X = Cl; R = Ph, X = Cl), (CabC,N)2Hg, and [(CabC,N)SnMe2]2. Organometallics 2005, 24, 58455852. (51) Kobayashi, K.; Nagase, S. Silicon−Silicon Triple Bonds: Do Substituents Make Disilynes Synthetically Accessible? Organometallics 1997, 16, 24892491. (52) Kobayashi, K.; Takagi, N.; Nagase, S. Do Bulky Aryl Groups Make Stable Silicon−Silicon Triple Bonds Synthetically Accessible? Organometallics 28 Environment ACS Paragon Plus

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2001, 20, 234-236. (53) Takagi, N.; Nagase, S. Substituent Effects on Germanium−Germanium and Tin−Tin Triple Bonds. Organometallics 2001, 20, 5498-5500. (54) The details about the theoretical methods used in this work are given in Supporting Information. (55) Liptrot, D. J.; Power, P. P. London Dispersion Forces in Sterically Crowded Inorganic and Organometallic Molecules. Nat. Rev. Chem. 2017, 1, 1-12. (56) Zhao, Y.; Truhlar, D. G. Density Functionals with Broad Applicability in Chemistry. Acc. Chem. Res. 2008, 41, 157-167. (57) Dudley, T. J.; Brown, W. W.; Hoffmann, M. R. Theoretical Study of HmGaPHn. Characteristics of Gallium−Phosphorus Multiple Bonds. J. Phys. Chem. A 1999, 103, 5152-5160. (58) Pykkö, P.; Desclaux, J.-P. Relativity and the Periodic System of Elements. Acc. Chem. Res. 1979, 12, 276-281. (59) Kutzelnigg, W. Chemical Bonding in Higher Main Group Elements. Angew. Chem. Int. Ed. Engl. 1984, 23, 272-295. (60) Pykkö, P. Relativistic Effects in Structural Chemistry. Chem. Rev. 1988, 88, 563-594. (61) Pyykkö, P. Strong Closed-shell Interactions in Inorganic Chemistry. Chem. Rev. 1997, 97, 597-636. (62) Sanderson, R. T. in Inorganic Chemistry, Reinhold, New York, 1967, p. 74. (63) The Wiberg bond index, which is used to screen atom pairs for the possible bonding in the natural bonding orbital (NBO) search, are performed with the NBO program. For details, see: http://www.chem.wisc.edu/~nbo5. (64) Wiberg, K. B. Application of the Pople-Santry-Segal CNDO Method to the Cyclopropylcarbinyl and Cyclobutyl Cation and to Bicyclobutane. Tetrahedron 1968, 24, 1083-1096. (65) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Intermolecular Interactions From a Natural BondOrbital, Donor-Acceptor Viewpoint Chem. Rev. 1998, 88, 899-926. 29 Environment ACS Paragon Plus


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(66) Dapprich, S.; Frenking, G. Investigation of Donor-Acceptor Interactions: A Charge Decomposition Analysis Using Fragment Molecular Orbitals. J. Phys. Chem. 1995, 99, 9352-9362. (67) The

CDA

results

concerning

the

(SiiPrDis2)−Ga≡P−(SiiPrDis2),

(Tbt)−Ga≡P−(Tbt), and (Ar*)−Ga≡P−(Ar*) molecules are given in Supporting Information. (68) Glendening, E. D. and Weinhold, F. Natural Resonance Theory: I. General Formalism. J. Comp. Chem. 1998, 19, 593-609. (69) Glendening, E. D. and Weinhold, F. Natural Resonance Theory: II. Natural Bond Order and Valency. J. Comp. Chem. 1998, 19, 610-627. (70) Glendening, E. D. Badenhoop, J. K.; Weinhold, F. Natural Resonance Theory: iii. Chemical Applications. J. Comp. Chem. 1998, 19, 628-646.


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TOC Graphic Triply Bonded Gallium≡Phosphorus Molecules: Theoretical Designs and Characterization Jia-Syun Lu, Ming-Chung Yang, and Ming-Der Su*


Triply Bonded Galliumâ¡Phosphorus Molecules: Theoretical Designs

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