Theme: Them's the Breaks - Target word(DEAL) is split with some letters stating a theme answer and the remaining letters closing the theme answer. Also known as bookends.
16A. *Kaput: DEAD AS A DOORNAIL
19A. *Life in a breakfast bowl, say: DRY CEREAL
22D. *Oral health care network: DELTA DENTAL
25D. Negotiations killer ... or, in a way, what each answer to a starred clue is: DEAL BREAKER
Argyle here with our award-winning constructor. The puzzle has vertical symmetry and one spanner.
1. The Bounty, e.g.: SHIP. There was a mutiny of the Bounty.
5. Remote control targets: TVs
8. Landowner's document: DEED
12. Subtle glow: AURA
13. Spruce oneself up: PRIMP. To titivate.
15. Addresses with forward slashes: URLs. (Uniform Resource Locator)
20. Move like a crab: SIDLE. Walk especially sideways or obliquely.
23. Often-stubbed digit: TOE
24. Black Russian liquor: VODKA. It's just vodka and Kahlua.
28. Nivea competitor: AVEENO. Skin care products. 63-Across. Body covering: SKIN
30. Invalidate, as a law: REPEAL
31. Rapper __ Wayne: LIL
32. Disney's title lamp rubber: ALADDIN
36. Sailor's agreement: AYE
37. Stage designs: SETS
39. Emulate flowers on a hot day: DROOP
40. Source of linen: FLAX
41. "Dilbert" creator Scott: ADAMS
43. "Little Women" woman: MEG. Meg, Jo, Beth and Amy.
44. Spongy cake laced with rum: BABKA
45. Scammer's targets: DUPEs
47. Step in a flight: STAIR
49. West Coast state: OREGON
51. Everglades waders: EGRETS
54. Layer of eggs: HEN
55. Target practice props: TIN CANS
59. "__ you awake?": ARE
60. Software test version: BETA
62. "M*A*S*H" actor Elliott: GOULD. From the movie. Trapper John.
64. Racetrack shape: OVAL
65. Homer Simpson's wife: MARGE. She of the blue hair.
66. Four-legged companions: PETS. Also known as our overlords.
67. Give a holler: YELL
68. In the future: AHEAD
69. Gratis: FREE
1. Pathetic: SAD
2. Tint: HUE
3. Nest egg acronym: IRA. (Individual Retirement Account)
4. Ping-Pong need: PADDLE
5. Piece of land: TRACT
6. Instagram upload: VIDEO
7. Messy campfire snack: S'MORE
8. Firestone competitor: DUNLOP
9. Pitching stat with a decimal point: ERA. In baseball statistics, earned run average (ERA) is the mean of earned runs given up by a pitcher per nine innings pitched (i.e. the traditional length of a game). It is determined by dividing the number of earned runs allowed by the number of innings pitched and multiplying by nine. TMI?
10. Inventor Whitney: ELI. Best known for inventing the cotton gin.
11. Broadband option, for short: DSL. (Digital Subscriber Line)
13. Maj. for a future shrink: PSY. Psychology.
14. "The 18-Down" poet: POE. 18-Down. "Nevermore" speaker: RAVEN
17. Structure with skyboxes: ARENA
20. Dip for chips: SALSA
21. Like the outfield walls at Wrigley Field: IVIED
26. Whitewater craft: KAYAK
27. Amazon Echo Dot's voice service: ALEXA
29. Well-worn: OLD
30. Harshly criticize: RIP. I had RAP crossing ALADAN. Oops.
33. Octopus' eight: ARMS
34. Deer mom: DOE
35. Dalmatians, e.g.: DOGS
38. Far from self-effacing: SMUG
40. Inside the foul line: FAIR
42. Dalmatian marking: SPOT
44. Hefty supplies?: BAGS. This could have been another baseball reference.
46. Hard puzzle: ENIGMA
48. Watched over: TENDED
49. "This could be a problem": "OH BOY"
50. Christopher of "Superman": REEVE
52. Done to death: TRITE
53. Sight or smell: SENSE
56. First matchmaker?: NOAH
57. Make better: CURE
58. Tiny pond growth: ALGA
61. "__ in favor, say 'aye'": ALL
63. Coppertone letters: SPF. (Sun Protection Factor)