-1 C C-
-2 i, gx, 3 B, 3 Al, 4 Si, 4 Sn, ZnX ard/soft () Ti, Cr, Ni, Pd, Pt, h, Cu, u, etc β-
1. Pauli und 2. SAB
(Atomic Orbital) z y z y z y z y x x x x s s p z p y p x p z y z y z x x y x x, y d xz d xy d yz d x 2-y2 d z 2 d
Density Density Density s 1s 2s 3s adial Distribution Function Distance adial Distribution Function Distance adial Distribution Function Distance y y y z z z x x x
Density Density Density p 2p adial Distribution Function 3p Distance adial Distribution Function z z y x y x y Distance 4p adial Distribution Function z z z y x y x y Distance
Density Density d 3d adial Distribution Function x 2 -y 2 z 2 Distance xy xz yz 4d adial Distribution Function x 2 -y 2 z 2 Distance xy xz yz
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 1 e 2 i Be B C N O F Ne 3 Na g Al Si P S Ar 4 K Ca Sc Ti V Cr n Fe Co Ni Cu Zn Ga Ge As Se Br Kr 5 b Sr Y Zr Nb o Tc u h Pd Ag Cd In Sn Sb Te I Xe 6 Cs Ba a f Ta W e Os Ir Pt Au g Tl Pb Bi Po At n 7 Fr a Ac f Db Sg Bh s t Ds g Unb Unt Unq Unp Unh Uns Uno a Ce Pr Nd Pm Sm Eu Gd Tb Dy o Er Tm Yb u Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm d No r s- p- d- f-
-1 1s 1 e 1s 2 i [e]2s 1 Be [e]2s 2 B [e]2s 2 2p 1 C [e]2s 2 2p 2 N [e]2s 2 2p 3 O [e]2s 2 2p 4 F [e]2s 2 2p 5 Na [Ne]3s 1 g [Ne]3s 2 Al [Ne]3s 2 3p 1 Si [Ne]3s 2 3p 2 S [Ne]3s 2 3p 3 P [Ne]3s 2 3p 4 [Ne]3s 2 3p 5 Ar [Ne]3s 2 3p 6 K Ca Sc Ti V [Ar]4s 1 [Ar]4s 2 [Ar]4s 2 3d 1 [Ar]4s 2 3d 2 [Ar]4s 2 3d 3 Cr [Ar]4s 1 3d 5 n Fe Co [Ar]4s 2 3d 5 [Ar]4s 2 3d 6 [Ar]4s 2 3d 7 Ni [Ar]4s 2 3d 8 Cu [Ar]4s 1 3d 10 Ga Ge As Se Br Kr [Ar]4s 2 3d 10 4p 1 [Ar]4s 2 3d 10 4p 2 [Ar]4s 2 3d 10 4p 3 [Ar]4s 2 3d 10 4p 4 [Ar]4s 2 3d 10 4p 5 [Ar]4s 2 3d 10 4p 6 und Ne [e]2s 2 2p 6 Zn [Ar]4s 2 3d 10
Density Density (Zeff) -1 i 1s, 2s 1s, 2s Z 2s = 1; Z 1s = 3 Z 2s = 1.28; Z 1s = 2.69 adial Distribution Function adial Distribution Function 1s 2s Distance Distance
(Zeff) -2 1s 2s 2s 1s 2s 1s 2s s 1s 2s 1s Z > 1 1s Z = 1 Z Z
(Zeff) -3 30.0 4s 3s, 3p 3d 22.5 3d 4s 15.0 3s 3d 4s 4p 7.5 3p 0 K Ca Sc Ti 3s 3d 4p V Cr n Fe Co Ni Cu Zn Ga As Ge Se Br Kr 3p 4s
Pauli und -1 1. Pauli 2. 3. und
Pauli und -2 Cr [Ar]3d 5 4s 1 4s 3d n [Ar]3d 5 4s 2 4s 3d 3d 4s Cu [Ar]3d 10 4s 1 3d 3d
Pauli und -3 3 4 5 6 7 8 9 10 11 12 4 21Sc 3d 1 4s 2 22Ti 3d 2 4s 2 23V 3d 3 4s 2 24Cr 3d 5 4s 1 25n 3d 5 4s 2 26Fe 3d 6 4s 2 27Co 3d 7 4s 2 28Ni 3d 8 4s 2 29Cu 3d 10 4s 1 30Zn 3d 10 4s 2 5 39Y 4d 1 5s 2 40Zr 4d 2 5s 2 41Nb 4d 4 5s 1 42o 4d 5 5s 1 43Tc 4d 6 5s 1 44u 4d 7 5s 1 45h 4d 8 5s 1 46Pd 4d 10 47Ag 4d 10 5s 1 48Cd 4d 10 5s 2 6 72f 5d 2 6s 2 73Ta 5d 4 6s 2 74W 5d 4 6s 2 75e 5d 5 6s 2 76Os 5d 6 6s 2 77Ir 5d 7 6s 2 78Pt 5d 9 6s 1 79Au 5d 10 6s 1 80g 5d 10 6s 2 5 6
(Ip) I p = E(A +, g) E(A, g) A A + Vapor Phase r = First Ip of the elements in ev, to convert kjmol -1, multiply 96.485 13.6 i 5.32 Na 5.14 K 4.34 b 4.18 Cs 3.89 Be 9.32 g 7.64 Ca 6.11 Sr 5.69 Ba 5.21 B 8.30 Al 5.98 Ga 6.0 In 5.79 Tl 6.11 C 11.26 Si 8.15 Ge 7.90 Sn 7.34 Pb 7.42 N 14.53 P 10.48 As 9.81 Sb 8.64 Bi 7.29 O 13.62 S 10.36 Se 9.75 Te 9.01 Po 8.42 F 17.42 12.97 Br 11.81 I 10.45 At 9.64 e 24.59 Ne 21.56 Ar 15.76 Kr 14.00 Xe 12.13 n 10.74
(Ea) A, r = E a = E(A, g) E(A, g) Vapor Phase A Electron affinities of the elements in ev, to convert kjmol -1, multiply 96.485 0.754 i 0.618 Na 0.548 K 0.502 b 0.486 Be <0 g <0 Ca 0.02 Sr 0.05 B 0.277 Al 0.441 Ga 0.30 In 0.3 C 1.263 Si 1.385 Ge 1.20 Sn 1.20 N -0.07 P 0.747 As 0.81 Sb 1.07 O 1.461 S 2.077 Se 2.021 Te 1.971 F 3.399 3.617 Br 3.365 I 3.059 e -0.5 Ne -1.2 Ar -1.0 Kr -1.0 Xe -0.8
Frontier Ip, Ea Frontier I p E a E a I p E a I p e UO E a I p OO i I p = E a? I p > E a
-1 Pauling ΔE (A-B) = E (A-B) 1/2x[E (A-A) + E (B-B) ] = K[X P (A) X P (B)] A-B ülliken X (A) = 1/2 [I P (A) + E a (A)] I p E a Pauling ülliken X P 1.35 (X ) 1/2 1.37
-2 2.20 3.06 e 5.5 i 0.98 1.28 Be 1.57 1.99 B 2.04 1.83 C 2.55 2.67 N 3.04 3.08 O 3.44 3.22 F 3.98 4.43 Ne 4.60 Na 0.93 1.21 g 1.31 1.63 Al 1.61 1.37 Si 1.90 2.03 P 2.19 2.33 S 2.58 2.65 3.16 3.54 Ar 3.36 K 0.82 1.03 Ca 1.00 1.30 Ga 1.81 1.34 Ge 2.01 1.95 As 2.18 2.26 Se 2.55 2.51 Br 2.96 3.24 Kr 3.0 2.98 b 0.82 0.99 Sr 0.95 1.21 In 1.78 1.30 Sn 1.96 1.83 Sb 2.05 2.06 Te 2.10 2.34 I 2.66 2.88 Xe 2.6 2.59 Cs 0.79 Ba 0.89 Tl 2.04 Pb 2.33 Bi 2.02 Pauling (X P, Plain) and ülliken (X, Bold)
X X (A) = 1/2 [I P (A) + E a (A)] F X i X 2s X X I p E a I p E a
Frontier Ip, Ea, X E a I p X UO X I p and E a OO, UO OO X I p and E a OO, UO
Group Electronegativity Group Electronegativity [calcd. by F/6-31G(d)] Group X Group X Group X -C 3 2.55 -C 2 O 2.59 -N 2 3.12 -C 2 =C 2 2.58 -C(=O) 2.60 -N3 + 3.21 -C C 2.66 -C(=S) 2.52 -NO 2 3.22 -C 3 2.70 -COO 2.63 -O 3.55 -CF 3 2.71 -CO 2.66 -O + 2 3.57 -Ph 2.58 -CN 2.69 -B 2 1.92 Boyd,. J. and Boyd, S.. J. Am. Chem. Soc. 1992, 114, 1652-1655.
SAB -1 ard/soft +1 ard +1 Soft ard acids + i + g + 21 pm 76 pm 119 pm Soft acids ard bases F Br I 133 pm 196 pm 220 pm Soft bases
SAB -2 The classification of ewis acids and bases ard Borderline Soft Acids +, i +, Na +, K +, Be 2+, g 2+, Ca 2+, Cr 2+, Cr 3+, Al 3+, SO 3, BF 3 and etc Bases F, O, 2 O, N 3, CO 3 2, NO 3, O 2, SO 4 2, PO 4 3+, O 4, Fe 2+, Co 2+, Ni 2+, Cu 2+, Zn 2+, Pb 2+, SO 2, BBr 3 and etc NO 2, SO 3 2, Br, N 3, N 2, C 6 5 N, SCN, Cu +, Ag +, Au +, Tl +, g +, Cd 2+, Pt 2+, g 2+, B 3 and etc,, CN, CO, I, SCN, P 3, C 6 6, S 2,
SAB -3 ard/soft ardness (η) = (I p E a )/2 Softness (σ) = 1/η η η A η B 6.4 i 2.4 Na 2.3 C 5.0 Si 3.4 N 7.3 P 4.9 O 6.1 S 4.1 F 7.0 4.7 + i + Na + Al 3+ Cu + 6.3 Cu 2+ Fe 2+ Fe 3+ g 2+ Pb 2+ Pd 2+ 35.1 21.1 45.8 8.3 7.3 13.1 7.7 8.5 6.8 F Br I C 3 N 2 O S CN 6.8 7.0 4.7 4.2 3.7 4.0 5.3 5.6 4.1 5.3 Parr,. G.; Pearson,. G. J. Am. Chem. Soc. 1983, 105, 7512.
Frontier Ip, Ea, X, η-1 E a I p X ard Energy Gap η igh UO and/or ow OO UO OO Soft Energy Gap ow UO and/or igh OO
(α, Polalizability) δ δ+ and/or ard O O Base pka > 50 O O E g (O) = 12.2 ev Base S S S S pka 31 and/or Soft E g (S) = 8.3 ev
VSEP -1 (Valens-Shell Electron Pair epulsion) (Shape) π CO 2 O 3 B 3 O C O O O O B AB 2 AB 2 E (A 3 E) AB 3 P
VSEP -2 N 3 2 O N O P Ph Ph Ph Sb Ph Ph AB 3 E AB 2 E 2 AB 5 F S F F F F F Br F F Xe F F F F Br F F F F Xe F F AB 4 E AB 3 E 2 AB 2 E 3 P eq AB 5 E AB 4 E 2 P ax
-1 Werner Werner 3 C C 3 3 C C 3 C O O Pt O O C 3 Py 3 C O N Pt O C eoc COe Pt(acac) 2 PtPy(acac) 2 Werner Werner N, O, X
1. X, ard or Soft, 2. ASB ard/soft 3. 4. 18
-1 X, X, F Br, (Alkyl), (Alkenyl), (Alkynyl), 2 N, O, O, CN, I, SO 3 2, NO 2, π, N 3, 2 O, O, O, P 3, CO, Alkene, Alkyne
-2 ASB ard ewis Base 2 O, O, N 3, N 2, O, F,, C 3 CO 2, SO 2 4, PO 3 4, O 4, NO 3, CO 3,..., etc (4 ) (4, 5 Soft ewis Base 2 S, S, I, CN,, (Alkyl), Alkene, Alkyne, S, P 3, CO, NC,..., etc (1, 2 ) (9 11 )
-1 Sc(d 1 s 2 ) Ti (d 2 s 2 ) V (d 3 s 2 ) Cr (d 5 s 1 ) +3(d 0 ) +4(d 0 ) +3(d 0 s 1 ) +4(d 1 ) +5(d 0 ), +3, +2 +3(d 3 ) +6(d 0 ), +2 d 0 n (d 5 s 2 ) +2(d 5 ) +7(d 0 ), +6, +4, +3, +2, -1 Fe (d 6 s 2 ) +3(d 5 ) +6 (s 2 ), +2, -2 d 5, d 10 Co (d 7 s 2 ) +2(d 7 or d 5 s 2 ) +3(d 5 s 1 ), -1 Ni (d 8 s 2 ) Cu (d 10 s 1 ) +2(d 8 or d 6 s 2 ) +2(d 9 or d 7 s 2 ) +3(d 5 s 2 ) +1(d 10 )
-2 /pm /pm V 5+ 54 V 2+ 79 Cr 6+ 26 Cr 3+ 61 n 7+ 25 n 2+ 83 Co 3+ 61 Co 2+ 75 ard Acid Soft Acid
-1 σ π
-2 A A d n A σ A=X C, F, CN, O, N 2 A= P 3, N 3, O 2, olefin
-3 X Cu I I ei Cu I e + ii ei e Cu I e i X Cu 1 Ni II 2 2PPh 3 Ph 3 P Ni II PPh 3 Ni 2
金属 配位子間結合-4 供与結合と逆供与結合 ホスフィン配位子 -1 空のd軌道 P 非共有電子対 P 充填されたd軌道 空の3d軌道 π-donor π-acceptor P 供与結合 σ-結合 P 逆供与結合 π-結合 逆供与結合は後期遷移金属 低原子価金属錯体の安定化に重要な働きをする
-5-2 P π- acidity Pe 3 P(N 2 ) 3 < PAr 3 < P(Oe) 3 < P(OAr) 3 < P 3 < PF 3 CO P- σ* Efficient Tunable igand
金属 配位子間結合-6 供与結合と逆供与結合 アルケン配位子 -1 結合性π軌道 空のd軌道 反結合性π*軌道 充填された d軌道 供与結合 逆供与結合
-7-2 C C d = 1.34 Å π π C C d = 1.40 ~ 1.47 Å Nu E ex) oechst-wacker
金属 配位子間結合-8 供与結合と逆供与結合 一酸化炭素 -1 O C 非共有電子対 空のd軌道 O C 反結合性軌道 充填された d軌道 O C 供与結合 O C 逆供与結合
-9-2 O C O C CO CO C δ+ π* O δ δ+ C O C O C O C O C O : : Zr (IV), d 0 complex Cp* 2 Zr(κ 2 -S 2 )(CO): ν(co) = 2057 cm -1 Ti(-II), d 4 complex [Ti(CO) 6 ] 2 : ν(co) = 1820 cm -1 C-O C-O
金属 配位子間結合-10 供与結合と逆供与結合 カルベン -1 Carbene Complex Fisher Type C n C 炭素ー金属二重結合を持つ C 供与結合 Singlet Carbene Schrock Type C C Triplet Carbene C C 逆供与結合 C 共有結合 x 2
-11-2 Fisher Carbene Schrock Carbene (OC) 5 W O C e Cp 2 Ta C Carbene Carbene π-acceptor CO π-donor -Oe, -N 2 δ+ Electrophylic π-acceptor, Cp, Alkyl π-donor Alkyl, δ Nucleophylic
金属 配位子間結合-12 π供与性結合 高酸化状態の前遷移周期金属に特有 Ti(O-iPr)4 O σ結合 全て空軌道 O O π結合 結合性相互作用 x 2 非共有電子対 後遷移周期 低原子価金属の場合 例 Pd(Oe)2は安定に存在するか 空軌道 O 非共有電子対 反発 充填された軌道 O 非共有電子対
-13 σ * d σ* d σ*
-1 18-1 8 (2s 2 + 2p 6 ) 18 ns 2 + np 6 + nd 10 Octet 18 18 Ni(II), Pd(II), Pt(II) 16 Cu, Ag, Au 14, 12 18 18 18
-2 18-2 -1 Ph 3 P Pd PPh 3 Ph 3 P PPh 3 10 10 2 x 4 = 8 18
-3 18-3 -2 3 N N Pt 3 Fe 10 2 8 2 x 2 + 2 x 2 = 8 N 3 8 2 6 2 x 2 + 2 x 4 = 12 16 18 σ X π
-4-1 iner (s, dz2) Trigonal (s, px, py) Tetrahedral (s, dxy, dyz, dxz) Square planar (s, px, py, dx2-y2) Square bipyramidal (s, px, py, pz, dz2) Trigonal bipyramidal (s, px, py, pz, dz2) Octahedral (s, px, py, pz, dz2, dx2-y2)
-5-2 inear ( 2 [Ag I (CN) 2 ] [Au I 2 ] d 10 Trigonal ( 3 gi 3 Fe 3, Pt 2 PPh 3 4 Fe Fe Ph 3 P Pt Pt PPh 3
-6-3 Trigonal bipyramidal( 5) Square bipyramidal ( 5) O 3 C O V O C 3 3 C O O C 3 VO(acac) 2
-6-4 Tetrahedral ( 4 Ti 4, no 4, Fe 4, CoBr 4, eo 4 Square Planar ( 4 Ni II, Pd II, Pt II, h I, Ir I d 8 Octahedral ( 6) Ti III, Cr III, n II, Fe II, Fe III, Co II, Co III, Ni II, Cu II, etc
-7
-8-1 z y (1) () x (2) () d y z z y z y x x y x x d xy d xz d yz d x2-y2 d z2 d d
-9-2 3d x 2-y2, 3d z 2 d 5 6 Dq 4 Dq 3d xy, 3d xz, 3d yz 10 Dq(Δo): Δ 0 (100 ~ 400 kj mol -1 ) I < Br < < F < O < 2 O < Py < N 3 < PPh 3 < CO < NO 2 < CN ow Δ 0 igh Δ 0 π- Donor π-acceptor / Strong σ-donor
-10-3 d 1 d 2 d 3 d 8 d 9 d 10 d 4 d 5 d 6 d 7
-11-4 d 4 Δ0 (und ) < n III (CN) 6 3+ Fe III (CN) 6 3+ d 4 (und ) > n III (acac) 3 Fe III (O 2 ) 6 3+
-12-5 z d xy, d yz, d xz 4 Dq x 6 Dq y y d x2-y2, d z2 x
-13-6 z y z d z2 : d xz, d yz ) x x, y d x2-y2 : d xy d x2-y2 d xy d z2 d yz, d xz d 8 Ni II, Pd II, Pt II d x2-y2 d 8
-7-14 12.28 d z2 10.28 9.14 6.0 7.07-5.46 d xz, d yz 1.14 1.78 0.86 2.28 d xy d x2-y2-6.28-0.82-2.67-2.72-4.00-0.86-4.57-3.21-3.86-4.28-5.14 inear Tetrahedral Octahedral Trigonal bipyramid Square pyramid Trigonal Square planar
-15 4p t1u 4s a1g 3d t2g & eg t1u* a1g* eg* dx2-y2 & dz2 dxy, dyz & dxz eg σ a1g, eg & t1u d xy, d yz, d xz (a 1g, t 1u, e g ) t1u a1g t 2g, e g* d
-1 Wacker Process (J. Smidt of Wacker Chemie, 1950s) Pd 2, Cu 2, O 2 O Pd 2 2 O 3 C 1 Wacker C3CO Pd(II) 2Cu(II) 1/2 O 2 C 2 4 Pd(0) 2Cu(I) 2 O
-2 Pd II 2 2 2 C C 2 Pd 2 Pd 2 O 2 O 2 O Pd O 2 O Pd Pd β O 2 O C 3 CO Pd Pd 2 O O 2 O 1,2- β 2 O Pd Pd 0 2 O 2 O Cu II Pd O Cu 0 Pd II
-1 n + S n-1 S + S: (16e ) S N 2 (18e) S N 1
-2 T X Y T Y X Y T X T Y Square Planar Square Planar Trigonal bipyramid Y (16e ) Y Y T X T X Tetrahedral Square Planar -24.56 Dq Tetrahedral -3.56 Dq d 8, 16e Square Planar -8
-3 Square Planar Pt 2- - N 3 N 3 Pt N 3 N Pt 3 N 3 3 N N 2+ Pt 3 3 N N 3 3 N N Pt 3 3 N + N Pt 3 3 N
-4 (Trans Influence ) t ' X - t - Y -X -Y O < 2O, N3 < < I, Br < CO, C24, < I < CN, P3 < C65, 3C, one Pair π-acceptor dπ
-5 t X 16e Y t X 18e t t Y Y X X Y t X t Y Y X t TBP sp 3 dz2 dxy, dyz, dxz, dx2-y2 dxy, dyz, dxz, dx2-y2 dπ dxy dx2-y2 xy equatrial π-acidic
-6 T X X T Square Pyramidal a Y b T Distorted trigonal bipyramidal a b T T Y et. X ate = k 1 [T 4 X] (18e) Y Inv. T Square Pyramidal T π Donor Distorted trigonal bipyramidal
-1 n + A B (Oxidative Addition) (eductive Elimination) n A B +2 +2 (1) (2) A-B A--B
-2 1. Concerted Addition 2. S N 2 Type Addition 3. adical echanism 4. Ionic echanism
-3 Concerted Addition (-, C-, Si-, C-C ) n + A B n A B n B A cis 16e, 0 18e, 0 18e, II CO Ph 3 P Ir PPh 3 Square planar 16e, Ir I 2 CO Ph 3 P Ir PPh 3 Ph 3 P Ir Trig. bipyramidal Octahedral 18e, Ir I 18e, Ir III CO PPh 3
-4 C-C, C-,, Pt 2 Py Py Pt Pt 2 n Py PPh 3 PPh 3 Ir PPh eat 2 Ir PPh 3 Ph 3 P Ph 3 P PPh 3 Ph 3 P Ir PPh 2
-5 S N 2 Type Addition (X, allyl-x, Benzyl-X, COX ) n C X n C X n C X Ni(P 3 ) 4 > Ni(PAr 3 ) 4 > Ni(PAr 3 ) 2 (alkene) > Ni(cod) 2 e-i > Et-I > i-pr-i -OTs > -I > -Br > -
-6 e Ph 3 Pd C X 2 XPd + eo O C 3 Pd e Ph C e Ph C eo + e - Ph X 2 XPd C 2 XPd O C e Ph C CO CO Ph 3 P Ir PPh 3 e-i e CO Ph 3 P Ir PPh 3 I e CO Ph 3 P Ir PPh 3 I
-7 adical echanisms (Pt, Ni ) PPh 3 Pt(PPh 3 ) 3 Pt(PPh 3 ) 2 16e, d 10 14e, d 10 SET Pt(PPh 3 ) 2 + X [Pt(PPh 3 ) 2 ] + [X] 14e, d 10 13e, d 9 [PtX(PPh 3 ) 2 ] + PtX(PPh 3 ) 2 16e, d 8 [PtX(PPh 3 ) 2 ] 15e, d 9 + e I > Br > >>OTs
-8 Ionic echanism( ) Ionic echanism( ) Pt(PPh 3 ) 4 18e, d 10, tetrahedral + PPh 3 Pt(PPh 3 ) 2 16e, d 8, Square Planar [Ir(cod) 2 ] + + [Ir(cod) 2 ] + + PPh 3 Pt(PPh 3 ) 3 16e, d 10, tetrahedral + c Fast PPh 3 [Pt(PPh 3 ) 3 ] + 16e, d 8, Square Planar Ir(cod) 2 18e, d 8, Trignalbipyramid
-9 A (eductive Elimination) n n + A B B d 8 : Ni II, Pd II, Au III d 6 : Pt IV, Pd IV, Ir III, h III 2 2 n n CO O C n ' ' n CO ' O C '
-10 Octahedtral -1 h - h h h 18e, d 6 Octahedral ilstein s Complex =Pe 3, =C 2 COe 16e, d 6 Trigonal bipyramid 16e, d 6 distorted TBP h 16e, d 8 Square Planar + h 14e, d 8 T shaped 3 coordinate
-11 Octahedtral P P e e Pt e I P = PPh 2 P P e e Pt e I P P I e e Pt e Pt IV, 18e, d 6 Octahedral Goldberg s complex e e e I P P Pt e I P P Pt e I P P Pt e e 16e, d 8 Square Planar 16e, d 8 Square Planar
-12 Square Planar X X X X 1. Dissociative echanism 2. Associative echanism 3. Nondissociative echanism
-13 Dissociative echanism Pd II, Au III X X X + Associative echanism Ni II X + X 3 + X X
-14 Nondissociative echanism 2 + + X X X X X X X X
-15 σ-bond ethathesis d 0 (Zr, W, etc) Cp 2 Zr + 2 Cp 2 Zr + Cp 2 Zr2 Zr Zr IV, 16e, d 0 Cp 2 Zr + 2 Cp 2 Zr + σ-bond ethathesis Cp 2 Zr Cp 2 Zr
-16 Oxidative Coupling & eductive Fragmentation Alkene π complex Oxidative Coupling eductive Fragmentation etalacycle ±2 ±0 cf. ±2 ±2 Cyclotrimerization of Alkynes C C 2 [OC] C C C C n n n C C [OC] [F] n C C n
-1 1,1-igratory Insertion 1,2-igratory Insertion O C 1,1- η 1 O C ±0 1 X C 2 C 2 1,2- β- 2 C η 2 X C 2 ydrogenation 1 3 1 3-2 4 Pd, h, 2 Ir, etc 4 ydroformylation 1 3-1 3 O CO C 2 4 h, Co, 2 etc 4
-2 e OC CO n CO CO CO CO or e CO n OC CO CO? CO O * CO e CO n OC CO CO CO O * CO e n CO CO CO O * CO e CO n OC CO e or CO shifts CO shifts e shifts OC e OC OC * CO n CO A * CO n e B CO CO CO CO A, B e shifts
-3 Pd II O 2 Pd O Pd II O 1,2-igratory Insertion Pd O D Pd II D O 2 CO Pd D O D O D O O D
-4 Na CO C 2 e CO2 e Soft Anion D Pd II D i e ard Anion Pd Ph D + ei Pd II (acac) 2 Ph e D β- elimination Ph 1,2-igratory D Insertion Ph D Pd e Pd e Ph Pd e D