DAEHAN HWAHAK HWOEJEE
(Journal of the Korean Chemical Society') Vol. 28, No. 1, 1984
Printed in the Republic of Korea
사각형〔 Pt(II)Cl(PEt3)2X 〕형태 착물의 계산한 쌍극자모멘트에 대한 리간드의 trans 효과 (X=H, M 에 iyl, Phenyl Group)
安商雲t •金東熙•朴義緖 전북대학교 자연과학대학 화학과
(1983. 6. 13 접수)
망 he trans Effect of Ligands on the Calculated Dipole Moments for Square Planar [Pt(II)Cl(PEt3 )2 Xj Type Complexes
(X=H, Methyl and Phenyl Group)
Sangwoon Ahn', Dong Heu Kim and Euisuh Park
Department of Chemistry, Jeonbug National University, Jeonju 520, Korea (Received June 13, 1983)
요 약. 加ms 사각형 [Pt(II)Cl(PEt3)2X]형태 착물을 택하여 계산한 쌍극자 모멘트에 대한 리간 드의 trans 효과를 고찰하여 보았다. 계 산한 쌍극자모멘트는 H〉Me〉Ph〉Cl 과 같은 순서 로 감소하 였다. 이 순서는 쌍극자모멘트의 실험치가 감소하는 순서와 일치하며 반응속도에 의하여 결정한 trans 효과가 감소하는 순서와도 일치한다. cis 착물의 계산한 쌍극자모멘트는 trans 착물의 계산한 쌍극자모멘트 보다 훨씬 크며 이것 또한 실험적 사실과 일치한다. 그러나 trans 착물의 경우와 달리 몇개의 cis 착물의 계산한 쌍극자모멘트는 실험치보다 작은 값을 가진다.
ABSTRACT. The trans effect of ligands on the cauculated dipole moments has been investigated, choosing trans square planar [Pt (II) Cl (PEt3) 2X] type complexes. The calculated dipole moments decrease in the order H〉Me〉Ph〉Cl which is the same as the order of dereasing the experimen
tal dipole moments. This order is in agreement with the order of decreasing the trans effect as determined by rate of reaction. The calculated dipole moments for cis complexes are markedly higher than those for trans complexes. This is also in agreement with experimental fact. The calculated dipole moments for some of cis complexes are, however, lower than the observed values, which is different from trans complexes.
INTRODUCTION
For a few decades considerable interest has been focussed on the cis and trans effects of ligands on ground state, thermodynamic and kinetic properties1, since the coordination of one ligand to metal ion influences the bonding between. that metal and every other ligand.
The cis and trans effects of ligands on the
ground state properties were observed by X-ray diffraction, vibrational spectroscopy and NMR technique2 and the trans effect of ligands on the thermodynamic properties was obtained from the gas phase enthalpy data. However, the kinetic effect of a trans ligand was first observed in preparative studies and it was found that the trans ligands have a profound effect on the reactivities and stabilities for square planar
3
complexes. 3,4 The measurement of the dipole moments has been widely used for determining structure of transition metal and organometallic complexes5, because the net dipole of a complex depends on the polarity and geometry of the ligands surrounding the metal ion. In this re
spect, we investigated the effects of the cis and trans configurations of ligands on the calculated dipole moments for octahedral (M (III) O3N3) and (NiQDOzNQ type complexes6.
The purpose of this work is to examine the trans effect of ligands on the calculated dipole moments for square planar (Pt (II) Cl (PEtg) 2X) type complexes, and to compare the theoretical order of decrease for the calculated dipole mo
ments with that for experiment. We adopt SCF wave functions7,8 which have integer values of n, I and m and then transform them into real forms.
EXTENDED HUCKEL(EHT) CALCULA
TION OF THE DIPOLE MOMENTS FOR SQUARE PLANAR LPt(II)Cl(PEt3)2X]
TYPE COMPLEXES
We choose, for example, square planar [Pt- (II)Cl(PEt3)2X] type complexes to investigate the trans effect of ligands on the calculated dip시e moments. 9,11 The orbital transformation schemes for these complexes are listed in Table 1. Here we assume that C^v symmetry is still maintained for [Pt (II) Cl (PEt3) 2X] type comp
lexes even though two or three different kind of ligands (group of atoms) occupy four edges of rectangle. Therefore, we adopt the modified approximate molecular orbitals of square planar complex12 and the notation of the C4v point group13. We also adopt the bondings of ligands as a linear combination of ns and npz orbitals of ligands and ms and (”z 一1)』； orbitals of platinum, respectively,
Fax (M) = sin涉(ms) ±cos^ (1) o (/) = sin^ (ns) ± cos^ (npz) (2) where 凯=6 and 戎=2 or 3.
The degree of hybridization is estimated by method described by Ballhausen and Gray13 This gives &=지4 for the sd£2 platinum hybrid orbital For the spz hybrid orbitals, 6 values are listed in Table 2. Here 0 is the angle at which the minimum values of VSIP (夕)/S (我) occur. VSIP (O') is the valence state ionization potential of valence orbitals of Pt (II) atom and hybrid orbitals of ligands, while S((9) is the overlap integrals of the valence orbital of Pt (II) with the appropriate hybrid orbital of ligands at angle 仇
It is stressed that following Pauling, o bonds only are assumed to be formed because such an assumption may precisely interpret the trans effect of ligands on the calculated dipole Table 1. Orbital transformation schemes for cis and trans square planar [Pt(II)Cl(PEt3)2X] type complexes
(a) trans square planar [Pt (II) Cl (PEta) 2H]
Irreducible
representation 匚(M) A(Z) 6s, 5d； 3 (ci+C<72 + Ciffa 4- C(?4)
bi 5（0一项 3-+ C“3 — Co%)
心） 6px
心） 6珏 /丄C02 — b4)
(b) cis square planar [Pt (II) Cl (PEts) 2H]
Irreducible
representation A(M) AW
ai 6s, 5d： -备01 + Cl<72 4- C《?3 + C&) bi — y2 专(E - Ci°2 + c內 一 C々，4)
e愆） 6%
◎ 6円 /丄(*丁2 - CQ
wi,prp c~ Electronegativity of P Electronegativity of Cl 公一 Electronegativity of H Electronegativity of Cl
사각형〔Pt（II）Cl（PEt3）2X〕형태 착물의 계산한 쌍극자모멘트에 대한 리간드의 trans 효과 5
(c) trans square planar [Pt (II) Cl (PEts) gMe]
Irreduci 비 e
representation 几(M)
6s, 5必 勇((71 + C<72 + + C<74) 5dz2_y2 会01 — C©2 + C% — C&4)
心） 6px /芸（。1-（；2°3）
心） 6% - ©4)
where C2=-/으뜨뜨空쁘쁘의一必皿 Electronegativity or Cl
(g) trans square planar [Pt(II) (PEt^Me?]
Irreducible
representation 几(M) 匚(I)
ai 6s, 5dz2 *(0]+CS2++CS4)
b\ 5d 了2一了2 芸(0] — CS2 + b3 — 必丁4)
心:） 6px /扑-。3）
e (:y) 6Py /壹。(02 —
where c，= ^ectronegat理ty。£ % Electronegativity oi C {sp^)
(d) cis square planar [Pt (II) Cl (PEtQ 2Me]
Irreducible
representation 匚・(M)
<21 6s, 5(0 -g-(<71 ++ Cg + C《M) bi 5d：f2_y2 3 01 一 c汐 2+Cff3 一 Cff4)
e愆） 6px 01 -〔％3)
。(:y) 6Py j如《切2-（如）
(h) cis square planar [Pt (II) (PEt3)2Me]
Irreducible
representation A(M) 如）
血 6s, 5dz2 ^(gi—az+C'om+C'oa) 5dx2_yi
心） 6px /奇心1 一 C“3）
e(y) 6p，， f (如-CS4)
(e) trans square planar [Pt (II) Cl (PEtg) sPh]
Irreducible
representation 儿(M) A(Z) 的 6s, 5dg2 * 0i + Gt2+C3173+C 赢)
5（Lt，2 書。(1 — C(72+Cg—C<?4)
。愆） /芸（叶-。3°3）
冷） 6p, |/ *C02 - °4)
(f) cis square planar [Pt (II) Cl (PE®) 2削]
Irreducible
representation A(Z)
6s, 5d22 芸(°1 + (爲宠 + C"3 + C<74) by 5dx2_j,2 3-(。"一C302 + C/3 — C/4) 心） 6务 传（饥一*3）
心） 6% 力4）
1 厂、 Electeonegativity of C(sp2) wherer Electron。응ati vity on of Cl
(i) trans [Pt(II)C12Me2]
Irreducible
representation 几(M) A（z）
ai 6s, 5dZ2 1/2
h 1/2 （。1一（；归2 +。‘3—（；2。4）
©3) 6px 1/ " 2 （。1一。3）
冷） 6Py 1/ / 2 (C2<?2 —C2(74)
(j) cis [Pt(II)Cl2Me2]
Irreducible
representation A(M) E
ai 6s, 5<侦 1/2 (<71 + C2 ~F ^2^3 + ^2^4) X 5（L：2 —〉，2 1/2 ((71—+ —C2<74) 冷） 6以 1/ V 2 (<71 —C2ff3) 心） 6py l/"2 (02一 C%)
moments for square planar platinum complexes.
Therefore, the a bonding molecular orbitals may be approximated as
如(MO) =NWi (M) + 伉匚。)} (3) 0*(MO) =M{a 产几(M) +ft*A(Z)} (4) where Ni and N* are normalization constants
Vol. 28, No. 1, 1984
6
Table 2. Degress of hybridization (^—degree)
Me (or ph) PEt3 Cl
sin。 cosO
e
sin^ cos。 0 sin。 cos5 6ai 0- 5150 0. 8572 31 0. 3907 0. 9205 23 0. 4607 0.9135 24
0- 2419 0. 9703 14 0. 2079 0. 9781 12 0.1736 0. 9848 10
e 0- 6157 0. 7880 38 0. 4540 0. 8910 27 0. 4384 0. 8988 26
for bonding and antibonding m시ecular orbitals given by
M=
{七2+2%・&V*M) IA(Z)>+A2)~4
<A(Z)|A©>}4
N；*= {a,*2+2a,•*&*</(M) |A(Z)>
"VW) l"〉3
The approximate energies and the correspond
ing eigenvectors of the molecuar orbitals are obtained by solving the following secular equation for square planar [Pt (II) Cl (PEt3) 2X]
type compexes,
In equation(5), the diagonal matrix elements are chosen as
H,j=—VSIP (6)
and the off-diagonal matrix elements H订 are calaulated using Ballhausen and Gray approxi
mation18,
H"=—KG,j(H,•，•瓦疽 (7)
where X=l. 6715. Since we choose the a bond
ing orbital for ligands as a hybridized atomic orbitals of ns and npz, the corresponding dia
gonal matrix element is then calaulated from, H0^-(sin2^(VSIP of ns) + cos2(9(VSIPof nPz)}
(8)
Group overlap integrals and estimated orbital energies for cis and trans square planar[Pt (II)- C1 (PEt3) 2X] type complexes are listed in Table 3. The geometric structures and energy level diagrams for cis and trans square planar
Table 3. Group overlap integrals and estimated energies for cis and trans square planar [Pt (II) Cl (PEta) 2XJ type complexes
(a) trans tPt(II)Cl(PEt3)2HJ
A (MO) G订 8(eV) % E「*(eV) %* ft*
0. 46299 一 26. 69 0.6068 0. 9512 -1.26 -0. 5622 0. 9781 0-13484 -19. 46 0.6860 0. 7402 一 L 80 0. 8260 -0. 5799
e(z) 0. 59122 一 37. 65 1. 0380 0. 6781 一 0.06 L 1606 -0. 4363
心） 0. 44042 -14. 01 0.6043 0. 9357 一 Q 83 -0. 5739 0. 9539
(b) cis [Pt(II)CI(PEt3)2H]
A (MO) G* 瓦・(eV) 皿
A
EL(eV)A*
说1 0. 46299 一 26. 99 0. 6 애68 0. 9512 -1. 26 -0. 5622 0. 9781
bi 0.13484 -19. 46 0. 6860 0. 7402 -1. 80 0. 8260 ~0. 5799
心 0. 52319 一 28. 59 0. 9520 0.6860 一 0. 54 1. 0827 -0. 4524
e(y) 0- 50841 -19. 59 0.9890 0. 6087 -0. 56 1. 0270 -0. 5422
Journal of the Korean Chemical Society
사각형 （Pt （II） Cl （PE® 2X〕형태 착물의 계산한 쌍극자모멘트에 대한 리간드의 〃•切 S 효과
(c) trans [Pt(II)Cl(PEt3)2Me]
G,, E(W) % ft E,*(eV) a{* A*
0- 43994 -26. 02 0. 6021 0. 9367 一 1. 54 一 0. 5763 0. 9528
h 0. 27540 一 18.60 0. 7662 0. 7035 —3- 52 0.8873 -0. 5429
心 0. 58367 一 39.23 1. 0181 0. 6930 一 0.11 1.1569 ~0. 4222
心） 0. 44042 一 14. 01 0.6043 0. 9357 -0. 83 -0. 5739 0. 9546
(d) cis [Pt(II)Cl(PEt3)2Me]
A (MO) G 瓦(eV) % ft 瓦* (eV) %* A*
0. 43994 -26. 02 0.6021 0.9367 一 L 54 -0.5763 0. 9528
bi 0.27540 -18. 60 0. 7662 0.7035 -3. 52 0.8873 -0. 5429
心） 0. 52319 -28. 59 0. 9520 0.6860 -0. 54 1. 0827 一 0. 4524
끼::y) 0. 50085 一 19. 29 0. 9811 0. 6102 一 0. 57 1. 0195 ~0. 5435
(e) trans [Pt (II) Cl (PEt3) 2Ph]
A (MO) Q.. 瓦(eV) <Xi ft 互 *(eV) %* A*
中 0. 45278 一 27. 49 0. 5922 0.9525 -1.43 -0. 6587 0.7622
代 0. 27900 -19. 09 0. 7639 0. 7077 -3. 50 0. 8928 -0. 5361
0. 60460 一 43. 44 1. 0470 0. 6920 0. 04 1.1848 -0. 4151
心） 0. 44042 -14. 01 0. 6043 0. 9357 -0. 83 -0. 5739 0. 9546
(f) cis [Pt(II)Cl(PEt3)2Ph]
A (MO) G.s E(eV) ft 瓦* (eV) &*
0. 45278 一 27. 49 0. 5922 0. 9525 -1.43 -0. 6587 0. 7622 成 0. 27670 -19. 09 0. 7639 0. 7077 一 3. 50 0. 8928 一 0. 5361
心） 0. 52319 一 28. 59 0. 9520 0. 6860 —0- 54 1. 0827 -0. 4524
心） 0. 52178 一 23. 52 0. 9876 0. 6420 -0. 49 1. 0594 -0. 5017
(g) trans EPt(n)Ph2(PEt3)2]
"(MO) G ■ 瓦(eV) 瓦 *(eV) a,* 乱*
的 0. 47410 -30. 79 0. 9674 0. 5951 一1. 28 0. 9826 -0. 5696
0.14290 -11.45 0. 7322 0. 6963 -5. 26 0. 7937 -0. 6252
心） 0. 60598 一 36. 46 1. 0720 0. 6372 0. 05 1.1723 -0. 5137
0. 49377 一 23. 51 0. 9341 0. 6707 -0. 71 1. 0445 -0. 4811
(h) Cis [Pt(II)Ph2(PEt3)2]____________________________
几(MO) G“ 瓦(eV) % A E 产(eV) a,* A*
幻 0. 47410 — 30. 79 0.9674 0. 5951 一1. 28 0. 9896 -0. 5696
h 6.14290 -11. 45 0. 7322 0. 6963 -5. 26 0. 7937 -0. 6252
0. 54989 -29. 70 0. 9933 0. 6685 -0. 34 1.1045 -0. 4620
心） 0. 54989 -29. 70 0. 9933 0. 6685 -0. 34 1.1045 -0. 4620
VgI. 28, No. 1, 1984
(i) trans [Pt(II)Cl2Me2]
A (MO) G.7 瓦(eV) % A E『(eV) %*
ai 0. 50506 -38. 49 0. 9739 0. 6276 -1. 06 1. 0336 -0. 5239
h 0.15242 -13. 81 0.6290 0. 7933 -5. 65 0. 8804 -0. 4999
心） 0.60598 -36.46 1. 0720 0. 6372 0. 05 1.1723 -0. 5137
끼3) 0. 56129 -29. 91 1. 0129 0. 6588 -0. 25 1.1138 -0. 4685
(j) cis EPt(II)Cl2Me2]
A (MO) G“ &(eV) <Xi A E") a,* 食*
a-i 0. 50506 一 38. 49 0.9739 0. 6276 -1.06 1. 0336 -0. 5239
h 0.15242 -13. 81 0.6290 0. 7933 -5. 65 0. 8804 -0. 4999
0- 58365 一 36.15 1. 0287 0. 6771 -0.11 1.1502 -0. 4401
心） 0- 59365 -36.15 1. 0287 0. 6771 -0.1 1.1502 -0. 4401
Pt (II) complexes are represented in Fig. 1 and 2, respectively.
The general formulas of the dipole moment matrix elements for bonding and antibonding molecular orbitals are
〈如(MO) IW(MO)〉
=N『｛2이务〈几(M) (씨이几《)〉｝
<0*(MO) I시由*(MO)〉
=1V严｛2叫当&*〈几(M) |r|AW>
+ &•"〈广 (Z)l 이/W)〉｝ (9) Applying the coordinate transformation sche
me for square planar complex to the approxi
mate molecular orbitals, we evaluate the dip시e moment matrix elements and then calculate the dipole moments for cis and trans square planar [Pt (II) Cl (PEt3)3Xj type complexes, using the assumptions adopted for transition metal comp- lexe소% from the following formula.
“=一2汕S(MO)IW(MO)〉 (10)
It is necessary here to mention that we adopt the transformation method of the dipole mo
ment matrix elements into overlap integrals to evaluate the dipole moment matrix elements of the approximate molecular orbitals for square
trans LPt(ll )CI(PEt3)2X] type complex
Fig. 1. Geometric structures of cis and trans square planar fPt (II) Cl (PEta) 2X] type complexes.
planar [Pt (II) Cl (PEt3)2X] type complexes16.
The required overlap integrals are listed in Appendix. The calculated dipole moments for cis and trans square planar [Pt(II)Cl(PEt3)2X]
type complexes are listed in Table 4.
THE trans EFFECT OF LIGANDS ON THE CALCULATED DIPOLE MOMENTS FOR SQUARE PLANAR rPt(n)Cl(PEt3)2X], TYPE COMPLEXES
Journal of the Korean Chemical Society
사각형〔Pt(II)Cl(PEt3)2X〕형 태 착물의 계산한 쌍극자모멘트에 대한 리간드의 切a* 효과 9
As shown in Table 4, the calculated dipole moments for trans [Pt (II) Cl (PEt3) 2X) type
complexes decrease in the order H〉Me〉Ph〉 CI which is the same as the order of decreasing
(a) tr이지(PEg)2H]
-jqU e(x)
e(y)
e(iy
(b) cis[Pt(ll)Cl(PEt3)2H]
-40*-
-40u
Fig. 2, Energy level diagrams for cis and trans (Pt(II)Cl(PEt3)2X) type complexes.
Vol. 28, No. 1, 1984
安商雲•金東熙•朴義緖
Fig. 2. Continue.
Tab# 4. The calculated dipole moments for cis and tram square planar (Pt(II)Cl(PEt3)2X) type complexes (unit： Debye)
Complex 缶 My Expl. values
iran4Pt(II)Cl(PEt3)2H] 4. 39 0 4. 39 4. 201
履 s[Pt(II)Cl(PEt3)2H] 5. 71 0. 49 5. 73
transit (II) Cl (PEt3)2Me] 3. 64 .0 3. 64 3. 409
3. 6 〜3. 7517
两[Pt(II)Cl(PEt3)2Me] 5. 37 1.90 5. 69 8. 409
Zran<Pt(n)Cl(PEt3)2Ph] 2. 74 0 2 74 2. 35〜2. 85u
n<Pt(II)Cl(PEt3)2Ph] 5. 36 2. 48 5. 90 6. 75-9.15】°
transit (II) Me2 (PEt3) 2] 0 0 0 0
«>[Pt(II)Me2(PEt3)2] 3. 00 3. 00 4. 24 5. 510, 5. 659
transit (II) Cl2Me2] 0 0 0 0
c?s[Pt(n)Cl2Me2j 3.56 3. 56 5. 04
Where the bond length is 사losen as a sum of covalent radii19.
사각형〔Pt(II)Cl(PEt3)2X〕형태 착물의 계산한 쌍극자모멘트에 대한 리간드의 trans 효과 11
the expermental dipole moments. Basolo, et al.
found that this decreasing order of the experi
mental dipole moments is in agreement with the order of decreasing the trans effect as de
termined by rate of reaction11. The calculated dipole moments for trans square planar [Pt(II)- C1 (PEt3)2X] type complexes are in resonable agreement with the experimental dipole momen
ts. As she ligand X has been displaced to the trans position, energy levels for cis square planar [Pt (II) Cl (PEt3) 2X] type complexes split as shown in Fig. 2. Especially, molecular orbital is stablized, while e(y) orbital is desta
bilized. Such a splitting of energy levels is the cis effect of ligands on the molecular orbital engergies. We can also find the cis effect of ligands on the calculated dipole moments be
cause the calculated dipole moments for square planar [Pt (II) Cl (PEt3) 2X] type complexes mar
kedly increase as the ligand X has been dis
placed to the cis position. However, we cannot find any regularity for the order of increas
ing the dipole moments as indicated experim
entally by Basolo, et al.11 The calculated dipole moments for some of cis square planar [(Pt (II)- C1 (PEts) 2X] type complexes are significantly lower than the experimental values.
As far as we are aware, no attempt has been made to perform molecuar orbital calcul
ation for heavy metal complexes and to calcu
late the dip시e moments for these complexes.
This work may thus be applied to evaluate the dipole moments for heavy metal complexes.
This work can also be applied to investigate the trans effect of ligands on the calculated dipole moments for tetrahedral and octahedral complexes.
APPENDIX
The requird overlap integrals are listed in the following.
<6s|2s)-(1/17280) (1/154)专？(1+£)13/2*(1一以5/2{瓦&+4&曷+4任&一，以533-10&&—4厶3位 +4々2五6+4&B7+AoJ%}
〈6s|3s〉= (1/34560) (1/1155)히：尸(1 + 以卩3/2[p(jT)貝气瓦瓦厂国&切 一財曲 — 6&84+64囱-「財3 反—3&&—&)&}
<6s|2p» = (1/5760) (1/462){-瓦曷 + &(&—5晶)+ &(5向-9為)+ &(9 B2~5B4) +5A4 (B3+B5) —A3 (5-B4 —9B6) —A2 (9B5—5B7) — A!(5B6—B8) —A0B7j
〈6s|3p》= (1/34560) (1/385)充P(l+Q]】3气p(lT)〃2{一&民 + &(反-4為)+4&(瓦-君3)-4&
(B2+B4) — 2^5(2B3—5B5) — 2A4 (5-B4—2B6) — 4A3 (55+B7) +4A2(B6~B8) +A1(4B7 — B9) +
〈61시2s〉= (1/5760) (1/462位尸(1+力】3/2*(17)5/2{48曷+&(&+3&) +&(35+瓦) +&(為— 58Q — 5A4(B3+B5) — &(5艮一位) +A2(B5+3B7) (3B6+B8)
+A
qB7]
<6pj3s>= (1/34560) (1/385)^P(1+?)]13/2[P(1-z)]7/2(719B1+A8(jBo+2B2)+2^7(81-83) ~2Ae(B2 + 3B4) — 6A5B3+6A4B6+2A3 (3B5+B7) +2A2(B6—B8) — A1(2-B7+Bg)
—A
qB^
〈6p/2pz〉= (1/5760) (1/154)如〉(1+如13/2"(1一項5/2{_瓦&—4&&+瓦(80—5反)+4虫瓦丄5&
(B2+B6) + 4^.3-®? ~ -^2 (5-B4—Bs) — 4A1B5—次&傀}
<6p213px> = (1/11520) (1/1155)牡(1+0丁3/2*(1顷2{_爲&-3&晶+ &(晶-BQ + 山6(3呂 + 5位) +A5(B2+5B6) -A^(5B3+Bi)-A3(5B4+3B8) +A2(B5-B9) +3^1B6+AoB7}
<7px|2s> = (1/241920) (l/143)^P(l+?)]15/2[P(l-Z)]5/2(^9B1+^8(B0+4B2)+4A7(B1+B3)+4A6(B2
V시. 28, No. 1, 1984
安商雲•金東熙•朴義緖
一瓦)-2氏(2&+5&) - 2瓦(5B4+
2B
q)
一 4& (& 一 B7) + 4A2 (B6 + B8) + & (4B7 + B9) 十 숴《成}⑺시3s〉= (1/241920) (l/1430)《[F(l+r)了5/2*(1_£)貝2 {&0务 + 爲(&+3晶) +348曷—8&&-2&
(4^3十3位) —・傀)+ 2& (3B5+4B7) + 8AaBg—3AiB9~Ai(3B8+B1())—厶凿拓
〈7p」2p» = (1/80460) (1/143)**(1+无項2*(1_如5/2{_爲&—5瓦&+&(&-昭)+5&(曷—
B5)+A5(9B2 + 5B6) +A4(5B3+9B7) -5^3(£4-£8) -^2(9B5-B9)
<7pj3p2> = (1/80460) (l/4290)*[F(l+£)丁5/2*(it)了4&氏 + &(瓦—4瓦)+4&㈤ +位)+2A(2B2+5B6) -4A5(B3~B7) —2A4(5B4+2B8)— 4^3(85+89) + yl2(4B6 — Blo) + 4&87+&_&}
2s〉= (1/483840) (5/143)兄P(l+t)丁孙頒^ — ^予勺一爲㈤—技会 + 瓦(9位+曷)+&(抨。+
10B2 + 3B4) +如6(331+283-585) + As (3B2 - 16B4 - 15B6) 一&(15& + 16BS - 3务)一 3A3 (5R - 2B6 - 3B8) + A2 (3Bs+10B7+3氏)+ & (9& + &) + Ao (3位—氏)}
<7M3s〉= (1/483840) (1/858)纪P(13)丁5气卩(1一力7/2{_&。(& —3晶)+2爲(曷 + 3&) +3As(B0 +382 — 284) +2A7(3B1-2B3-9B5) -2A6(3B2+11B4) -18A5(B3- B7) +2A4(llB6+358) + 2禹(9Bs+2B7—3B9) + 3A2 (2B6 一 3B8 一 Blo) - 2& (3B7+爲)一 & (3位—Blo))
〈7d/|2p》= (1/484840) (15/143)*P(l + £)了5/2*(1_力5/2{爲(島_333)-瓦(&-332+12瓦)- A7(.3B1-2B3+15B^)+A6(3B0-2B2~Bi)+As,(il2B1+Bs+15B7)+A7(15B2+B6+12Bs)-
A3 (&+2B7 - 3Bg) -A2(15B4- 2B6 + 3B8) 一 & (12&—3B7+Bg) 一 Ao (3彘一位)}
〈7<*|3p〉= (1/485040) (1/286)-物(1+Q丁以仍—庁/气—侦察-如-瓦(為-2矽+9反)- Ag (2Bi+&+3位)+ A7 (3B0+B2-3B4 + 153Q + A6 (9Bi+3B3+B5 +15B7) + As (3B2 -易
+B6-3B
s)
- A4(15B3+B5+3B7+9Bg) -A3(15B4-3B6+BS+3B10) +A2(3BS + B7 + 2B9) + & (9B6 - 2BS+B10) + Ao (3B7 -氏)}〈7s 12s〉= (1/241920) (1/143)#[F(1+，)了5气的_£)]5/2{&囱+54内+8&14&瓦-14&曷+
8A2B7 + 5爲氏+&)&}
<7이3務 = (1/241920)(1/4290)**(1 + £庁5/2眾17)了/2四囱+4爲务 + 招辺2-8&33—14&& + 14&一傀+8厶3务-3&冼-4&& ~瓦五的}
<652s〉= (1/34560)(1/22)虹％1*)〕13/2*(1_由5/2{_爲(3务_533)十&(3反-6&-5瓦)+2&
(3B1+6&—5&) -&(5反+12為—15B4—103Q + 5A4-3B3-3B5+B7) 一&(10剧+15位 -12B6-5B8) -2A2(5B3-6B5~3B7') +Ai(i5Bi+6B6-3Bg) +yl0(5B5-3B7))
〈6履13s〉=(1/69020) (1/165)汕(1 +洱3/2[(piT)y/2{—爲(3角_5瓦)_3&(&-昭)+3&(3曷+
2B3~5B5)+A6{5B0+6B2-27Bi)-3A5(9B3-5B7)-3A4(5B2-9B6) +A3(,27Bi-QB7-5B9) + 3A2 (5瓦—2B6 一 3B8) + 3為㈤-3呂)一 & (5&—3反)}
<6f?|2Pz)-(1/34560) (3/22)汕(1 + 勿13/2*(1)]5/2{瓦(3為-5瓦)+2&(33-昭)-& (3&+
5BQ -2^5(-81-55?) +5Ai(B0+B2+B6+Ba) +A3(5B1-B7) ~A2(.5Bi+3Bs) -2A(553-
&) 一厶0(5艮—3&)
<6f』3p〉= (1/69120) (1/55)牝P(l+t)丁3/2*(it)]〃2{位伽2-5岛)一％&+5电 一&(3&+7瓦 -10&) + &； (Bi+5曷+103» +(5反+7爲+5& - 5&) + A4 (5曷 一 5氏 一 7B7 一 5位) - A3 (1()及+5瓦+&)-A2(10B3-7B5-3B9) +&(5瓦+彘)+A0(5B5-3B7)}
사각형〔Pt(II)Cl(PEt3)2X〕형태 착물의 계산한 쌍극자모멘트에 대한 리간드의 trans 효과 13
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Vol. 28, No. 1, 고 984
![Fig. 1. Geometric structures of cis and trans square planar fPt (II) Cl (PEta) 2X] type complexes.](https://thumb-ap.123doks.com/thumbv2/123dokinfo/5027140.551791/6.918.54.715.192.860/fig-geometric-structures-trans-square-planar-peta-complexes.webp)
![The Effects of the cis and trans Configurations of Ligands on the Calculated Dipole Moments for $[M(II)O_3N_3]$ and $[Ni(II)O_2N_4]$ Type Complexes](data:image/gif;base64,R0lGODlhAQABAIAAAP///wAAACH5BAEAAAAALAAAAAABAAEAAAICRAEAOw==)